CN100433447C - Storage battery system,regeneration storage battery system and automobile - Google Patents

Abstract

Translated fromChinese

本发明提供一种降低了高温环境下的再生充电那样的高温环境下的急速充电时的电池膨胀的再生用蓄电系统。其特征在于包括：以非水电解质蓄电池为单位单元并且通过再生电力进行充电的电池组(3)，该非水电解质蓄电池具备包含锂钛复合氧化物的负极层、包含载置上述负极层的集电体的负极；在上述电池组的温度大于等于45℃小于等于90℃时，将上述单位单元的最大充电终止电压V₁(V)控制在下式(1)的范围内的充电控制装置(4)，其中，V₀表示在25℃将上述电池组充满电时的上述单位单元的最大充电终止电压(V)，0.85×V₀≤V₁≤0.96×V₀(1)。

The present invention provides a regenerative power storage system that reduces battery expansion during rapid charging in a high-temperature environment, such as regenerative charging in a high-temperature environment. It is characterized in that it includes: a battery pack (3) that uses a non-aqueous electrolyte storage battery as a unit unit and is charged by regenerative power, and the non-aqueous electrolyte storage battery has a negative electrode layer containing a lithium-titanium composite oxide; The negative electrode of the electric body; when the temperature_of the above-mentioned battery pack is greater than or equal to 45°C and less than or equal to 90°C, the charge control device (4 ), where V₀ represents the maximum end-of-charge voltage (V) of the unit cell when the battery pack is fully charged at 25°C, 0.85×V₀ ≤V₁ ≤0.96×V₀ (1).

Description

Accumulating system, regeneration storage battery system and automobile

Technical field

The present invention relates to be suitable for to improve energy efficiency is the battery system of the regeneration storage battery system that is used for automobile (from motor-car), cart, electric car, elevator, wind power generation etc. of purpose.

Background technology

In recent years, for effective use of energy sources, use the renewable energy resources effectively flexibly, and studied hybrid vehicle (from motor-car) that battery is installed, cart, electric car, elevator, wind power generation etc., and made its a part of practicability according to environmental cure.The battery of practicability and installation is lead accumulator and Ni-MH battery till now.

But, for example for the Ni-MH battery that is used for hybrid vehicle, following problem is arranged, i.e. when height is exported or rapidly sharply heating during charging (regeneration), and the very big thermal degradation when of generation.

Therefore, according to Ni-MH battery, research installation thermal degradation when is little and can carry out the lightweight of battery pack, the lithium ion battery of thin typeization, but the problem of cell expansion distortion under high temperature environment such as summer is arranged.

In patent documentation 1, put down in writing the charge-discharge controller that possesses with lower member: under the temperature of the storage battery situation more than or equal to the temperature of regulation, the control charge-discharge electric power makes and is no more than the predetermined charge-discharge electric power higher limit that changes accordingly with temperature.

Patent documentation 1: the spy opens the 2003-219510 communique

Summary of the invention

Purpose of the present invention just is: the regeneration that a kind of cell expansion when having reduced charging rapidly under the such hot environment of the refresh charging under the hot environment is provided with accumulating system and accumulating system, possess the automobile (from motor-car) of above-mentioned regeneration with accumulating system or above-mentioned accumulating system.

Regeneration of the present invention is characterised in that with accumulating system and comprises: be unit cell with the non-aqueous electrolyte battery, by the battery pack that regenerated electric power charges, this non-aqueous electrolyte battery possesses the negative electrode layer that comprises lithium-titanium composite oxide, the negative pole that comprises the collector body of the above-mentioned negative electrode layer of mounting; In the temperature of above-mentioned battery pack more than or equal to 45 ℃ during smaller or equal to 90 ℃, with the maximum charge final voltage V of above-mentioned unit cell₁(V) be controlled at battery charge controller in the scope of following formula (1),

0.85×V₀≤V₁≤0.96×V₀ (1)

Wherein, V₀Be illustrated in the maximum charge final voltage (V) of 25 ℃ of above-mentioned unit cells when above-mentioned battery pack is full of electricity.

Accumulating system of the present invention is characterised in that: possess the battery pack of the unit cell of being made up of non-aqueous electrolyte battery, this non-aqueous electrolyte battery possesses the negative electrode layer that comprises lithium-titanium composite oxide, the negative pole that comprises the collector body of the above-mentioned negative electrode layer of mounting, positive pole, nonaqueous electrolyte; Be used to measure the temperature sensor of the temperature of above-mentioned battery pack; Be used to measure the potentiometer of the voltage of above-mentioned unit cell; In the temperature of above-mentioned battery pack more than or equal to 45 ℃ during smaller or equal to 90 ℃, with the maximum charge final voltage V of above-mentioned unit cell₁(V) be controlled at battery charge controller in the scope of following formula (1),

0.85×V₀≤V₁≤0.96×V₀ (1)

Wherein, V₀Be illustrated in the maximum charge final voltage (V) of 25 ℃ of above-mentioned unit cells when above-mentioned battery pack is full of electricity.

Automobile of the present invention (from motor-car) is characterised in that: possess above-mentioned regeneration with accumulating system or above-mentioned accumulating system.

Above-mentioned regeneration with accumulating system or above-mentioned accumulating system in, it is desirable to above-mentioned battery charge controller when the temperature of above-mentioned battery pack is controlled the charging capacity of above-mentioned battery more than or equal to 45 ℃ during smaller or equal to 90 ℃, with above-mentioned maximum charge final voltage V₁(V) be controlled in the scope of above-mentioned formula (1).

In addition, according to the invention provides a kind of regeneration accumulating system, it is characterized in that comprising: be unit cell with the non-aqueous electrolyte battery, by the battery pack that regenerated electric power charges, this non-aqueous electrolyte battery possesses the negative electrode layer that comprises lithium-titanium composite oxide, the negative pole that comprises the collector body of the above-mentioned negative electrode layer of mounting; More than or equal to 45 ℃ during smaller or equal to 90 ℃, the control charge volume makes the end of charge voltage V of above-mentioned unit cell in the temperature of above-mentioned battery pack₁(V) satisfy the battery charge controller of following formula (1),

0.85×V₀≤V₁≤0.96×V₀ (1)

Wherein, V₀Be illustrated in the end of charge voltage (V) of 25 ℃ of above-mentioned unit cells when above-mentioned battery pack is full of electricity.

According to the present invention, the regeneration that a kind of cell expansion when having reduced charging rapidly under the such hot environment of the refresh charging under the hot environment can be provided with accumulating system and accumulating system, possess the automobile of above-mentioned regeneration with accumulating system or above-mentioned accumulating system.

Description of drawings

Fig. 1 is the ideograph of the regeneration storage battery system of expression one embodiment of the present of invention.

Fig. 2 is the cut-away section oblique view of unit cell of the battery pack of expression pie graph 1.

Fig. 3 is the flow chart of the regeneration of presentation graphs 1 with the action of accumulating system.

Fig. 4 is the block diagram of the detailed relation of the battery pack of presentation graphs 1 and battery control unit.

Fig. 5 is the exploded perspective view of the employed battery component of battery system (pack) of embodiment 1 andembodiment 2.

Fig. 6 is the block diagram of electric circuit of the battery component ofpresentation graphs 5.

Fig. 7 is the cut-away section oblique view of another example of the platypelloid type non-aqueous electrolyte battery of the pattern ground expression battery component that is used for Fig. 5.

Fig. 8 is the amplification sectional view of the A part of Fig. 7.

Embodiment

(embodiment 1)

Present inventors have studied following problem, promptly when the battery pack of the non-aqueous electrolyte battery that possesses the negative pole that comprises lithium-titanium composite oxide in negative electrode active material is implemented refresh charging, the reason that battery pack expands if depth of charge is deepened in continuation at high temperature is: the lithium of lithium-titanium composite oxide comprises unit to the side displacement, the reduction decomposition unit of the nonaqueous solvents in the nonaqueous electrolyte is to the master displacement simultaneously, both sides' potential difference reduces, by the reaction of nonaqueous solvents and lithium-titanium composite oxide, produce gas.

So, found following situation: by in the temperature of battery pack more than or equal to 45 ℃ during smaller or equal to 90 ℃, the control charge volume makes that the maximum charge final voltage V1 (V) in the closed circuit of above-mentioned unit cell satisfies following formula (1), thereby the battery pack that reduces to regenerate with accumulating system expands.

0.85×V₀≤V₁≤0.96×V₀ (1)

Wherein, V₀Be illustrated in the maximum charge final voltage (V) in the closed circuit of 25 ℃ of above-mentioned unit cells when above-mentioned battery pack is full of electricity.At this, be full of electricity condition and be meant the rated capacity that is charged to battery pack.The rated capacity of battery pack is meant the discharge capacity of discharging under the current value suitable with the 0.2CmA of the charging capacity that designs.

Maximum charge final voltage V1 and maximum charge final voltage V0 are the magnitudes of voltage that expression constitutes the unit cell of the maximum charge final voltage in all unit cells of battery pack.

Has distribution owing to constitute its capacity of unit cell and the resistance of above-mentioned battery pack, so the charging voltage of unit cell creates a difference when battery pack is full of electricity.Therefore, capacity the charging voltage little or unit cell that resistance is big becomes the maximum charge final voltage easily.Therefore, in order to keep the high life performance of battery system, importantly under the maximum charge final voltage of unit cell, control.

If maximum charge final voltage V1 (V) has surpassed 0.96 * V0, then the lithium of the lithium-titanium composite oxide difference that comprises the reduction decomposition unit of unit and nonaqueous solvents reduces, and produces a large amount of gas, and battery pack expands.On the other hand, if maximum charge final voltage V1 (V) less than 0.85 * V0, charging capacity deficiency then, the output characteristic of battery pack reduces.Owing to above reason, maximum charge final voltage V1 (V) is defined as the scope of above-mentioned formula (1).Better scope is 0.9 * V0≤V1≤0.96 * V0.

By using aluminium foil or alloy foil as negative electrode collector, can improve the exothermicity of negative pole, and the uniformity of the Temperature Distribution in the raising unit cell, the temperature that therefore can reduce between the discrete and unit cell of temperature in the unit cell is discrete, can improve the charge and discharge circulation life of battery pack.If the rated capacity of unit cell increases, then Re distribution departs from easily, therefore in this case, uses aluminium foil or alloy foil more to produce effect.

In addition, by as negative electrode collector, use the average crystallite particle diameter smaller or equal to the aluminium foil of 50 μ m or average crystallite particle diameter alloy foil smaller or equal to 50 μ m, can improve the exothermicity and the chemical stability of negative pole, gas generated in the time of therefore can further reducing refresh charging at high temperature.

Below, with reference to Fig. 1 one embodiment of the present of invention are described.

Fig. 1 is the ideograph of regeneration storage battery system 1, accumulating system 101 and the automobile (from motor-car) 102 of expression one embodiment of the present of invention, Fig. 2 is the cut-away section oblique view of unit cell of the battery pack of expression pie graph 1, Fig. 3 is the action flow chart of presentation graphs 1 regeneration storage battery system, and Fig. 4 is the block diagram of the detailed relation of the battery pack of presentation graphs 1 and battery control unit.

This regeneration storage battery system 1 mainly is made of accumulating system 101, motor andgenerator 5, and motor is connected with the wheel 103 of automobile 102 via axletree 104 grades with generator 5.In addition,, also can drive, can also as hybrid automobile, use internal combustion machine 105 to drive simultaneously with the motor portion of motor andgenerator 5 for the wheel 103 that drives automobile 102.Accumulating system 101 possesses:booster mechanism 2,battery pack 3 that is connected withbooster mechanism 2 and the battery control unit (BMU) 4 that is connected with battery pack 3.Battery pack 3 is a unit cell with slim non-aqueous electrolyte battery, possesses the module that a plurality of unit cells are together in series or parallel.Fig. 2 has represented an example of slim non-aqueous electrolyte battery.Electrode group 1 has the structure that helical form is circled round, and making becomes flat pattern acrossspacer 14 betweenpositive pole 12 and negative pole 13.For example makeanodal 12 andnegative pole 13 between circle round and after becoming flat pattern,, makeelectrode group 11 acrossspacer 14 helical forms by implementing heating and pressurizing.Thepositive pole 12 ofelectrode group 11,negative pole 13 andspacer 14 can become one by the macromolecule with cementability.Strip-shapedpositive electrode terminal 15 is electrically connected with anodal 12.On the other hand, Dai Zhuannegative terminal 16 is electrically connected with negative pole 13., under the state ofcontainer 17 protrusions, thiselectrode group 11 is contained in the stacked film container made 17 in the end that makespositive terminal 15 and negative terminal 16.In addition, by heat seal stacked film container made 17 is sealed.

Battery control unit (BMU) 4 possesses as shown in Figure 4: the temperature sensor (for example thermocouple, thermistor etc.) 6 that is used to measure the temperature ofbattery pack 3; Be used to measure thepotentiometer 7 of battery voltage and unit cell voltage; Be used to measure thegalvanometer 8 of the electric current of battery pack; Charge-discharge control circuit 9a; Charge cutoff circuit 9b; Circuit 9c is cut off in discharge.

Charge-discharge control circuit 9ainput temp transducer 6,potentiometer 7 andgalvanometer 8 measurement result separately.Can signal be input to charge cutoff circuit 9b and discharge cut-out circuit 9c according to this input signal, control discharging and recharging of battery pack 3.Specifically, charge-discharge control circuit 9a is provided with charged state (SOC) according to measurement result, and its result is sent to charge cutoff circuit 9b and discharge cut-out circuit 9c.Charge cutoff circuit 9b or discharge are cut off circuit 9c and can be calculated in order to obtain the necessary charging capacity of set SOC.Under the situation of Fig. 1,9b calculates by the charge cutoff circuit.Result of calculation is sent to charge-discharge control circuit 9a.If charging capacity has reached the value of regulation by discharging and recharging ofbattery pack 3, then signal is input to charge cutoff circuit 9b and discharge cut-out circuit 9c from charge-discharge control circuit 9a, stop charging and discharge, SOC can be controlled to be the value of regulation.

Such regeneration storage battery system 1 is connected withgenerator 5 with DC motor as the automobile (from motor-car) of load.As automobile, for example can enumerate two and take turns to the hybrid vehicle of four-wheel and electric motor car etc.The generator that is connected with DC motor is connected with the booster mechanism of regeneration storage battery system 2.Booster mechanism 2 plays a role as charger from regenerated electric power tobattery pack 3 that supply with.On the other hand, DC motor is connected with the BMU4 of regeneration storage battery system.Thus, can with the signal that cuts off circuit 9c from charge cutoff circuit 9b and discharge accordingly, the output of control frombattery pack 3 to DC motor.

The action of this regeneration storage battery system 1 is described with reference to Fig. 3.

The driving of the DC motor by hybrid vehicle etc. supplies tobattery pack 3 after being boosted bybooster mechanism 2 by the electric power of generator for electricity generation.Under the situation ofbattery pack 3 charging (input),, and its result sent to charge-discharge control circuit 9a at any time by the temperature (S1) oftemperature sensor 6monitor battery pack 3 of the BMU4 of regeneration storage battery system 1.In charge-discharge control circuit 9a, if the temperature ofbattery pack 3 less than 45 ℃, is then charged up to being full of electricity or becoming the charged state (SOC) of regulation, complete charge (S2).In addition, if the temperature ofbattery pack 3 surpasses 90 ℃, then cut off circuit 9c transmission signal to charge cutoff circuit 9b and discharge, charging (input), discharge (output) become the state (S3) of standby (stopping).Consequently battery stops heating, and battery temperature is cooled to less than 45 ℃.It is desirable tobattery pack 3 is cooled to smaller or equal to 30 ℃.

On the other hand, the temperature ofbattery pack 3 more than or equal to 45 ℃ and smaller or equal to 90 ℃ situation under (S4), send the signal that charging (input) or discharge (output) begin from BMU4 to battery pack 3.Thus, can be controlled to be the charged state (SOC) of regulation, V1 is set in the scope of above-mentioned formula (1) simultaneously.The charged state that it is desirable to stipulate (SOC) is to be full of 60～90% of electricity.

In BMU4, the voltage and current ofmonitor battery pack 3 and unit cell (S6).In charge-discharge control circuit 9a, maximum charge final voltage V1 in the closed circuit of unit cell and the maximum charge final voltage V1 that is input to BMU4 are in advance compared, the moment in maximum charge final voltage V1 reaches the scope of above-mentioned formula (1) is to chargecutoff circuit 9a output signal (S7), complete charge (S8).

According to said system, the maximum charge final voltage V1 of unit cell is converged in the scope of above-mentioned formula (1), and suppress the temperature rising of the battery pack of charging, the therefore expansion of the battery pack that can suppress to charge.In addition, control charging capacity by discharge, so system and uncomplicated, and can positively maximum charge final voltage V1 be maintained in the scope of above-mentioned formula (1).

In addition, in above-mentioned regeneration storage battery system shown in Figure 1, cooling fan is not installed, battery pack is cooled off but can import cooling fan etc. yet.In this case, better is the charged state (SOC) that is controlled to be regulation, make above-mentionedbattery pack 3 temperature more than or equal to 45 ℃ and smaller or equal to 60 ℃ V1 in the scope of formula (1).Temperature in battery pack surpasses under 60 ℃ the situation, it is desirable to make discharge and recharge the state that becomes standby (stopping), and is cooled to smaller or equal to 30 ℃.By this control, can further improve the life performance of battery pack, can suppress the decline of output performance simultaneously.

In addition, also can replace DC motor and use alternating current motor.But, need rectifier in this case.

Below, negative pole, positive pole, spacer, nonaqueous electrolyte and the container of slim non-aqueous electrolyte battery are described.

(1) negative pole

This negative pole has negative electrode collector; Be positioned on the one or both sides of negative electrode collector, comprise the negative electrode layer of negative electrode active material, conductive agent and bonding agent.

As negative electrode active material, use the material that comprises lithium-titanium composite oxide.For example can enumerate lithium titanate (spinel-type Li for example as lithium-titanium composite oxide_4+xTi₅O₁₂, wherein x is-1≤x≤3, it is desirable to 0＜x＜1) etc.On the cycle performance this point, it is desirable to lithium titanate especially.This is because the lithium of lithium titanate comprises unit for about 1.5V, for aluminium foil collector body or alloy foil collector body, is material highly stable on the electrochemical.

As lithium-titanium composite oxide, except the lithium titanate of above-mentioned spinel-type, can also use for example Li_2+xTi₃O₇The oblique ashlar type lithium titanate of (x is-1≤x≤3) etc.The lithium titanate and the oblique ashlar type lithium titanate of spinel-type are referred to as Li-Ti oxide.As lithium-titanium composite oxide, except this Li-Ti oxide, can also use the titanium-containing oxide that does not comprise lithium.As titanium-containing oxide, can enumerate and comprise from by TiO₂, at least a metal element composite oxides selected among the group that forms of Ti and P, V, Sn, Cu, Ni, Fe etc.It is desirable to TiO₂The heat treatment temperature that is Detitanium-ore-type is 300～500 ℃ a low-crystalline material.As comprising from by TiO₂, at least a element selected among the group that forms of Ti and P, V, Sn, Cu, Ni, Fe composite oxide of metal, for example can enumerate TiO₂-P₂O₅, TiO₂-V₂O₅, TiO₂-P₂O₅,-SnO₂, TiO₂-P₂O₅-MeO (Me is at least a element of selecting from the group who is made up of Cu, Ni, Fe) etc.It is desirable to this composite oxide of metal and be that crystallinity is low, the microstructure of crystalline phase and amorphous phase coexistence or amorphous phase individualism.By such microstructure, can increase substantially cycle performance.Wherein, it is desirable to comprise the composite oxide of metal of at least a element of from the group of forming by Li-Ti oxide, Ti and P, V, Sn, Cu, Ni, Fe, selecting.

For negative electrode active material, except lithium-titanium composite oxide, can also comprise the negative electrode active material of other kinds.As other negative electrode active materials, for example can enumerate the carbonizable substance that comprises and discharge lithium.

The average particulate diameter that it is desirable to negative electrode active material is smaller or equal to 1 μ m.By using the negative electrode active material of average particulate diameter, can improve cycle performance smaller or equal to 1 μ m.Particularly when charging rapidly and during high output discharge, its effect is remarkable.This be because: for example for the negative electrode active material that comprises and discharge lithium, particle diameter is small more, and then the diffusion length of the lithium ion of active material inside is short more, and the schedule of proportion area is big more.Better is that average particulate diameter is smaller or equal to 0.3 μ m.But if average particulate diameter is little, then particle is easy to generate aggegation, might cause the uniformity of negative pole to reduce, and therefore it is desirable to lower limit more than or equal to 0.001 μ m.

It is desirable to by the reaction of carrying out the active material raw material synthetic, as the powder of active material presoma making smaller or equal to 1 μ m, use pulverizers such as ball mill or injector-type mill, carry out pulverization process and become firing powder after the processing, thereby obtain the negative electrode active material of average particulate diameter smaller or equal to 1 μ m smaller or equal to 1 μ m.

Measure the particle diameter of negative electrode active material by the following method: use laser diffraction formula distribution of particles measurement mechanism (Tianjin, island SALD-300), after at first in beaker, adding the distilled water and abundant stirring of about 0.1g test portion, surfactant, 1～2mL, be injected into and stir in the tank, with 2 second measuring space light echo intensity distributions, the analysing particulates distributed data.

It is desirable to form negative electrode collector with aluminium foil or alloy foil.In addition, it is desirable to the average crystallite particle diameter of aluminium foil or alloy foil smaller or equal to 50 μ m.Better is that the average crystallite particle diameter is smaller or equal to 10 μ m.For the high more superior conductivity of Chemical Physics intensity that obtains the more little then negative electrode collector of average crystallite particle diameter, it is desirable to microscopic structure is crystalline, and the lower limit that therefore it is desirable to the average crystallite particle diameter is 0.01 μ m.

Be set to improve the intensity of aluminium foil or alloy foil by the average crystallite particle diameter smaller or equal to 50 μ m tremendously.By increasing this negative electrode collector intensity, physical chemistry patience strengthens, and can reduce the disrumpent feelings of negative electrode collector.Can prevent from especially under hot environment in the long-term cycle of overdischarge under (more than or equal to 40 ℃) can to suppress the increase of electrode resistance because of the dissolving of significant negative electrode collector, the deterioration that corrosion causes.And then by suppressing the increase of electrode resistance, Joule heat reduces, and can suppress the heating of electrode.

In addition, by increasing negative electrode collector, even anticathode applies high pressure, collector body can be not disrumpent feelings yet.Thus, can make the negative pole densification, improve capacity density.

Generally, when electrode was exerted pressure, the average particulate diameter of negative electrode active material was more little, and then the load of anticathode collector body is big more.By with average particulate diameter smaller or equal to the aluminium foil of 50 μ m or average particulate diameter smaller or equal to the alloy foil of 50 μ m as negative electrode collector, make negative electrode collector tolerance because of average particulate diameter smaller or equal to the negative electrode active material of 1 μ m produce electrode is exerted pressure the time strong load, the negative electrode collector in the time of therefore can avoiding exerting pressure disrumpent feelings.

In addition, by the densification of negative pole, pyroconductivity increases, and can improve the exothermicity of electrode.And then, by heating that suppresses electrode and the cumulative effects that improves the exothermicity of electrode, can suppress the rising of battery temperature.

The complex effects that the scope of average particulate diameter is subjected to material composition, impurity, processing conditions, heat treatment resume and many factors such as heating condition of firing and cooling condition smaller or equal to aluminium foil or the alloy foil of 50 μ m, in manufacturing process, organically make up above-mentioned each factor ground above-mentioned crystalline particle diameter is adjusted.In addition, can make negative electrode collector by the paper tinsel system PACAL21 that uses Japan's system.

Specifically, can make the aluminium foil of average particulate diameter as follows smaller or equal to 50 μ m: after the aluminium foil that under 50 ℃～250 ℃ to average particulate diameter is 90 μ m carries out annealing in process, cool to room temperature.On the other hand, can make the alloy foil of average particulate diameter as follows smaller or equal to 50 μ m: after the alloy foil that under 50 ℃～250 ℃ to average particulate diameter is 90 μ m carries out annealing in process, cool to room temperature.

Measure the average particulate diameter of aluminium foil and alloy foil by the method for following explanation.With the tissue on metal microstructure sem observation negative electrode collector surface, in the visual field of 1mm * 1mm, measure the crystalline particle that exists and count n, and calculate average grain area S (μ m by following formula (2)²).

S＝(1×10⁶)/n (2)

At this, with (1 * 10⁶) expression value be visual field area (the μ m of 1mm * 1mm²), n is the average grain number.

Use resulting average grain area S, calculate average particulate diameter d (μ m) according to following formula (3).5 positions (5 visuals field) carried out the calculating of such average particulate diameter d, and with its mean value as average particulate diameter.Presumptive error about 5%.

d＝2(S/π)^1/2 (3)

The thickness that it is desirable to negative electrode collector is smaller or equal to 20 μ m.The purity that it is desirable to aluminium foil is more than or equal to 99.99%.As above-mentioned aluminium alloy, it is desirable to comprise the alloy of elements such as magnesium, zinc, manganese, silicon etc.On the other hand, it is desirable to transition metal amounts such as iron, copper, nickel, chromium smaller or equal to 100ppm.

Can use material with carbon element as conductive agent.For example, can enumerate acetylene black, carbon black, coke, carbon fiber, graphite etc.

As bonding agent, for example can enumerate polytetrafluoroethyl-ne alkynes fiber (PTFE), polyfluoro acetylene fork (PVdF), fluorine element is rubber, butadiene-styrene rubber etc.

The mix proportion of active material, conductive agent and bonding agent that it is desirable to negative pole is in the scope of negative electrode active material 80～95 weight %,conductive agent 3～18 weight %,bonding agent 2～7 weight %.

For example make negative pole: make negative electrode active material, conductive agent and bonding agent outstanding turbid in appropriate solvent, this outstanding absurd creature is applied on the collector body of aluminium foil or alloy foil, carry out drying and exert pressure as follows.

The thickness that it is desirable to negative electrode active material layer is that the one side of each negative electrode collector is 5～100 μ m.Especially if the scope of 5～50 μ m, therefore the heat conductivity of the negative pole in the time of then can improving discharging and recharging under the big electric current can suppress rapid heating.

(2) positive pole

This just has: positive electrode collector; Be positioned on the one or both sides of above-mentioned positive electrode collector, comprise the anodal layer of positive active material, conductive agent and bonding agent.

As positive electrode collector, can enumerate aluminium foil or alloy foil, the same with negative electrode collector, it is desirable to the average crystallite particle diameter smaller or equal to 50 μ m.Better is smaller or equal to 10 μ m.Scope by average particulate diameter is set to can increase the intensity of aluminium foil and alloy foil smaller or equal to 50 μ m tremendously, can make anodal densification under high pressure, can improve capacity density.The more little generation that then can reduce hole and crack more of average particulate diameter, the while can be improved the chemical strength and the physical strength of positive electrode collector.For as have crystalline collector body microscopic structure and guarantee the appropriateness hardness, the lower limit that it is desirable to average particulate diameter is set to 0.01 μ m.

The thickness that it is desirable to positive electrode collector is smaller or equal to 20 μ m.

Can enumerate oxide, sulfide, polymer etc. as positive active material.

For example, can enumerate for example MnO as oxide₂Manganese dioxide, iron oxide, cupric oxide, nickel oxide, for example Li_xMnO₂O₄Or Li_xMnO₂Deng complex Li-Mn-oxide, for example Li_xNiO₂Deng lithium nickel composite oxide, for example Li_xCoO₂Deng lithium cobalt composite oxide, for example LiNi_1-yCo_yO₂Deng lithium/nickel/cobalt composite oxide, for example LiMn_yCo_1-yO₂Deng lithium manganese cobalt composite oxide, for example LiMn_2-yNi_yO₄Deng spinel type lithium manganese cobalt composite oxide, for example Li_xFePO₄, Li_xFe_1-yMn_yPO₄, Li_xCoPO₄Deng Lithium Phosphor Oxide, for example Fe with olivine structural₂(SO₄)₃Deng ferric sulfate, for example V₂O₅Deng barium oxide etc.In addition, the not special record of x, y it is desirable to 0～1 scope.

For example, as polymer, can enumerate conductive poly condensation materials such as many aniline or Polypyrrole, disulfides polymeric material etc.Other can also use sulphur (S), fluorocarbons etc.

As desirable positive active material, can enumerate complex Li-Mn-oxide, lithium nickel composite oxide, lithium cobalt composite oxide, lithium/nickel/cobalt composite oxide, spinel type lithium mn-ni compound oxide, lithium manganese cobalt composite oxide, lithium ferric phosphate etc.They can obtain high cathode voltage.Wherein, if use complex Li-Mn-oxide, lithium nickel composite oxide, lithium cobalt composite oxide, lithium/nickel/cobalt composite oxide, lithium manganese cobalt composite oxide, then can suppress the reaction of positive active material under the hot environment, negative electrode active material and nonaqueous electrolyte, can increase substantially battery life.

In addition, it is desirable to use Li_aNi_bCo_cMn_dO₂The lithium nickel manganese cobalt composite oxide of (wherein mol ratio a, b, c and d are 0≤a≤1.1, b+c+d=1) expression.By using lithium nickel manganese cobalt composite oxide, can access high cell voltage.The better scope of mol ratio a, b, c and d is 0≤a≤1.1,0.1≤b≤0.5,0≤c≤0.9,1≤d≤0.5.

As conductive agent, can enumerate for example acetylene black, carbon black, graphite etc.

As bonding agent, for example can enumerating, polytetrafluoroethyl-ne alkynes fiber (PTFE), polyfluoro acetylene fork (PVdF), fluorine element are rubber etc.

The mix proportion that it is desirable to positive active material, conductive agent and bonding agent is in the scope of positive active material 80～95 weight %,conductive agent 3～18 weight %,bonding agent 2～7 weight %.

For example make positive pole: make positive active material, conductive agent and bonding agent outstanding turbid in appropriate solvent, this outstanding absurd creature is applied on the collector body of aluminium foil or alloy foil, carry out drying and exert pressure as follows.

The thickness that it is desirable to positive electrode active material layer is that the one side of each positive electrode collector is 5～100 μ m.Especially if the scope of 5～50 μ m, therefore the heat conductivity of the positive pole in the time of then can improving discharging and recharging under the big electric current can suppress rapid heating.

(3) spacer

As spacer, can enumerate for example synthetic resin system adhesive-bonded fabric, polyethylene multiple aperture plasma membrane, polypropylene multiple aperture plasma membrane etc.

(4) nonaqueous electrolyte

As nonaqueous electrolyte, can enumerate aqueous nonaqueous electrolyte by electrolyte dissolution is modulated in the organic solvent, with above-mentioned aqueous electrolyte and macromolecular material carry out after compound the gel nonaqueous electrolyte or with the solid nonaqueous electrolyte after lithium salts electrolyte and compoundization of macromolecular material.In addition, also can use the normal temperature fuse salt (the ionic body that melts) that comprises lithium ion.

By with the concentration of 0.5～2mol/L with electrolyte dissolution in organic solvent, modulate aqueous nonaqueous electrolyte.

As electrolyte, for example can enumerate LiClO₄, LiPF₆, LiBF₄, LiAsF₆, LiCF₃So₃, LiN (CF₃SO₂)₂, LiN (C₂F₅SO₂)₂, Li (CF₃SO₂)₃C, LiB[(OCO)₂]₂Deng.Employed electrolytical kind can be a kind of 2 kinds or more than.

As organic solvent, for example can enumerate lock such as trimethylene carbonic ester (PC), acetylene carbonic ester cyclic carbonates such as (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Methylethyl carbonic ester (MEC) shape carbonic ester, dimethoxy acetylene (DME), acetal acetylene (DEE) and wait lock shape ethers, oxolane (independent or mixed solvent such as cyclic ether, gamma-butyrolacton (GBL), methane cyanide acetonitrile (AN), sulfone (SL) such as THF), dioxolane.If use the nonaqueous electrolyte comprise GBL, gas generated in the time of then can further reducing charging.Except GBL, if comprise from the group who forms by PC and EC, select at least a then better.

As macromolecular material, for example can enumerate polyfluoro acetylene fork (PVdF), polyacrylonitrile (PAN), polyoxyethylene (PEO) etc.

In addition, above-mentioned normal temperature fuse salt (the ionic body that melts) is made of lithium ion, organic substance cation and organic substance anion, during smaller or equal to 100 ℃, also is liquid when it is desirable to be lower than room temperature.

(5) container

As container, except above-mentioned stacked film container made shown in Figure 2, can also use the metallic container.As shape, can enumerate pancake, dihedral, cylindrical shape, coin shape, button shape, film shape, stacked shape, be installed in large-sized battery in electric automobile etc. etc.

As stacked film, for example can enumerate the multilayer film that comprises metal level and cover the resin bed of metal level.For lightweight, it is desirable to metal level is aluminium foil or alloy foil.Resin bed is used for metal level is carried out reinforcement, can use polypropylene (PP), polyethylene (PE), polyamide, polyethylene terephthalate macromolecules such as (PET) to form.

For example can melt bonding patch laminate film, obtain the stacked film container made by heat.

The ideal range of the thickness of stacked film is smaller or equal to 0.5mm.In addition, the lower limit that it is desirable to the thickness of stacked film is 0.01mm.

It is desirable to the metallic container is formed by aluminum or aluminum alloy.It is desirable to aluminum or aluminum alloy average particulate diameter separately smaller or equal to 50 μ m.Be set to can increase smaller or equal to 50 μ m the intensity of the metallic container that is made of aluminum or aluminum alloy by average particulate diameter, the thickness of attenuate container is guaranteed sufficient mechanical.Thus, can improve the exothermicity of container, therefore can suppress the rising of battery temperature.In addition, by improving energy density, can make battery lightweight and miniaturization.In addition, better is smaller or equal to 10 μ m.For the high more superior conductivity of Chemical Physics intensity that obtains the more little then container of average particulate diameter, it is desirable to microscopic structure is crystalline, and the lower limit that therefore it is desirable to average particulate diameter is 0.01 μ m.

These features are suitable for the battery of requirement hot conditions, high-energy-density etc., for example storage battery loaded onto vehicle.

The ideal range of the thickness of slab of metallic container is smaller or equal to 50mm.In addition, the lower limit that it is desirable to the thickness of slab of metallic container is 0.05mm.

The purity that it is desirable to above-mentioned aluminium foil is more than or equal to 99.99%.As above-mentioned aluminium alloy, it is desirable to comprise the alloy of elements such as magnesium, zinc, manganese, silicon etc.On the other hand, it is desirable to transition metal amounts such as iron, copper, nickel, chromium smaller or equal to 100ppm.

Can carry out sealing of metallic container by laser.Therefore, compare, can reduce the volume of hermetic unit, can improve energy density with the stacked film container made.

(embodiment 2)

The battery system of embodiment 1 has more than the situation of charging by regenerated electric power that is limited to, and also can be suitable under more than or equal to 45 ℃ hot environment the situation of charging rapidly.As such purposes, the light vehicle of power supply usefulness, bicycle etc. that can enumerate digital camera is with the backup battery (UPS does not have the power failure power subsystem) of power supply, personal computer or factory, dust catcher etc.

The battery system ofembodiment 2 can be the structure the same with the battery system of the foregoing description 1 except do not use regenerated electric power in charging.It is desirable to charge rate is more than or equal to 2C, smaller or equal to 120C.At this, 1C is meant 1 hour and makes the unit cell desired current value that discharges, and the value of the metric system capacity of unit cell can be replaced into the 1C current value for convenience.

In the battery system of embodiment 1 andembodiment 2, can usebattery pack 3 and battery control unit (BMU) 4 are contained in the interior battery component of a housing.In the battery system ofembodiment 2, owing to do not need to import by regenerated electric power, so can use battery component itself as battery system.The configuration example of battery component is described with reference to Fig. 5 and Fig. 6.Fig. 5 is the exploded perspective view of the employed battery component of battery system of embodiment 1 andembodiment 2, and Fig. 6 is the block diagram of electric circuit of the battery component ofpresentation graphs 5.

Theunit cell 21 of the battery component of Fig. 5 is made of platypelloid type non-aqueous electrolyte battery shown in Figure 2.It is that a ground is stacked on thickness direction that a plurality ofunit cells 21 make the protrusion direction unification ofpositive terminal 15 and negative terminal 16.As shown in Figure 6,unit cell 21 is connected in series and becomes battery pack 3.Battery pack 3 becomes one by splicingtape 23 as shown in Figure 5.

The rated capacity that it is desirable tounit cell 21 is more than or equal to 2Ah, smaller or equal to 100Ah.The better scope of rated capacity is more than or equal to 3Ah, smaller or equal to 40Ah.And then, in the hybrid vehicle time spent, it is desirable in used for electric vehicle and UPS time spent, it is desirable to the rated capacity smaller or equal to 40Ah more than or equal to 15Ah more than or equal to 3Ah, smaller or equal to the rated capacity of 15Ah.At this, rated capacity is meant the capacity when discharging under 0.2C speed.

The number ofunit cell 21 it is desirable to more than or equal to 5 and smaller or equal to 500, and the better scope of number is smaller or equal to 200 more than or equal to 5.And then, hybrid vehicle with and the electric automobile time spent, it is desirable to more than or equal to 5 smaller or equal to 200, in the UPS time spent, it is desirable to more than or equal to 5 smaller or equal to 1000.In addition, when vehicle mounted, in order to obtain high voltage,unit cell 21 it is desirable to be connected in series.

Relativepositive terminal 15 andnegative terminal 16 side of protruding and dispose printed circuit board 24.As shown in Figure 5, themeasurement component 25a,protective circuit 26 of thermistor and to theterminal 27 of external equipment energising usefulness is installed on printedcircuit board 24.

Themeasurement component 25b of thermistor can be to whole configurations of a plurality ofunit cells 21, also can be to the unit cell configuration arbitrarily in a plurality of unit cells 21.Under situation, must theunit cell 21 in the stage casing that is positioned atbattery pack 3 be provided with themeasurement component 25b of a part ofunit cell 21 configuration thermistors.To the situation of themeasurement component 25b ofwhole unit cells 21 configuration thermistors with only under the situation to part configuration, maximum detected temperatures is the temperature of battery pack 3.In addition, it is desirable tothermistor measurement component 25b the central authorities that the position is the planar section ofunit cell 21 are set.As detection signal, the measurement result of thermistor is sent toprotective circuit 26.

As shown in Figure 5 and Figure 6, thewiring 28 of the side of the positive electrode ofbattery pack 3 is electrically connected with the side of thepositive electrode connector 29 of theprotective circuit 26 of printed circuit board 24.Thenegative side wiring 30 ofbattery pack 3 is electrically connected with thenegative side connector 31 of theprotective circuit 26 of printedcircuit board 24.

Protective circuit 26 possesses charge-discharge control circuit, charge cutoff circuit, discharge cut-out circuit, potentiometer,galvanometer.Unit cell 21 is connected with thewiring 32 that is used to detect voltage and current separately, and by thesewirings 32 detection signal is sent to protective circuit 26.Be connected with external loading with charger with terminal 27 with the energising of external equipment.

Protective circuit 26 not only plays a role as battery control unit, the also following effect of performance: under defined terms, cut-off protection circuit 26 and and the energising of external equipment withpositive side wiring 31a between the terminal 27 andminus side wiring 31b, guarantee fail safe.Defined terms is meant when for example the detected temperatures of thermistor becomes more than or equal to set point of temperature, when detecting the overcharging ofunit cell 21, overdischarge, overcurrent etc. etc.All carry out this detection method at eachunit cell 21 or at unit cell 21.Under the situation that detects eachunit cell 21, can detect cell voltage, also can detect anodal current potential or negative pole current potential.In the latter case, in eachunit cell 21, insert the lithium electrode that uses as with reference to the utmost point.

Forbattery pack 3, threediaphragms 33 that the sides configuration is made of rubber or resin beyond the side ofpositive terminal 15 andnegative terminal 16 protrusions.Between the side and printedcircuit board 24 ofpositive terminal 15 andnegative terminal 16 protrusions, dispose theprotection piece 34 of the bulk that constitutes by rubber or resin.

Thisbattery pack 3 is contained in eachdiaphragm 33,protection piece 34 and printedcircuit board 24 in thestorage container 35 simultaneously.That is,diaphragm 33 is configured in two medial surfaces of long side direction ofstorage container 35 and the medial surface of short side direction respectively, printedcircuit board 24 is configured in the medial surface of the opposition side of short sidedirection.Battery pack 3 is positioned at the space that is fenced up bydiaphragm 33 and printed circuit board 24.With thelid 36 be installed instorage container 35 above.

In addition, for fixing ofbattery pack 3, can replacesplicing tape 23 and the use shrink belt.In this case, diaphragm is configured in the two sides of battery pack, after twining shrink belt, makes this shrink belt thermal contraction, finish battery pack.

In addition, theunit cell 21 shown in the Fig. 5 that is connected in series, 6, but in order to increase battery capacity, also can be connected in parallel.Certainly, also the battery component series, parallel after the assembling can be connected.

In addition, the employed platypelloid type non-aqueous electrolyte battery of battery component has more than and is limited to above-mentioned structure shown in Figure 2, for example also can be Fig. 7 and structure shown in Figure 8.Fig. 7 is the cut-away section oblique view of another example of the platypelloid type non-aqueous electrolyte battery of the pattern ground expression battery component that is used for Fig. 5, and Fig. 8 is the amplification sectional view of the A part of Fig. 7.

As shown in Figure 7, in the container 17 of stacked film system, accommodate cascade type electrode group 18.Cascade type electrode group 18 as shown in Figure 8, have make anodal 12 and negative pole 18 betwixt across the alternately laminated structure in spacer 14 ground.Anodal 12 exist a plurality ofly, possess positive electrode collector 12a respectively and the positive active material that is positioned on the two sides of positive electrode collector 12a contains a layer 12b.Negative pole 13 exists a plurality of, possesses negative electrode collector 13a respectively and the positive active material that is positioned on the two sides of positive electrode collector 13a contains a layer 13b.It protrudes the negative electrode collector 13a of each negative pole 13 from anodal 12 on one side.Be electrically connected with the negative terminal 16 of band shape from the anodal 12 negative electrode collector 13a that protrude.The front end of banded negative terminal 16 reaches the outside from container 17.In addition, on this not shown ground, protrude from negative pole 13 on be positioned at and the limit of the protrusion limit opposition side of negative electrode collector 13a of anodal 12 positive electrode collector 12.The positive electrode collector 12a that protrudes from negative pole 13 is electrically connected with strip-shaped positive electrode terminal 15.The front end of strip-shaped positive electrode terminal 15 is positioned at and negative terminal 16 opposition sides, reaches the outside from the limit of container 17.

[embodiment]

Below, describe embodiments of the invention in detail with reference to above-mentioned accompanying drawing.In addition, only otherwise exceed aim of the present invention, then the present invention has more than and is limited to the following embodiment that discloses.

(embodiment 1)

The negative pole manufacture method is described.Make lithium titanate (Li as the average particulate diameter 0.3 μ m of active material₄Ti₅O₁₂), as the carbon dust of the average particulate diameter 0.4 μ m of conductive agent, to become weight ratio as the polyfluoro acetylene fork (PVdF) of bonding agent be like that to cooperate at 90: 7: 3, and be distributed in n-methyl pyrrolidone (NMP) solvent, after modulating paste, being applied to thickness is the alloy foil (purity is 99.4%) of the average particulate diameter 50 μ m of 12 μ m, dry also through the pressurization operation, produce electrode density 2.4g/cm³Negative pole.In addition, by under 200 ℃, the alloy foil (purity 99.4%) ofthickness 12 μ m, average particulate diameter 90 μ m carried out annealing in process after, cool to room temperature, and make negative electrode collector.

Anodal manufacture method is described.Make lithium and cobalt oxides (LiCoO as the averageparticulate diameter 3 μ m of active material₂), as the powdered graphite of electric conducting material, become weight ratio as the polyfluoro acetylene fork (PVdF) of bonding agent and like that cooperate at 87: 8: 5, and be distributed in n-methyl pyrrolidone (NMP) solvent, after modulating paste, being applied to thickness is the aluminium foil (purity is 99.99%) of theaverage particulate diameter 12 μ m of 15 μ m, dry also through the pressurization operation, produce electrode density 3.5g/cm³Positive pole.In addition, by under 140 ℃, the aluminium foil (purity 99.99%) ofthickness 15 μ m, average particulate diameter 90 μ m carried out annealing in process after, cool to room temperature, and make positive electrode collector.

Container has used the stacked film that contains aluminium of thickness 0.1mm.This its thickness of aluminium lamination that contains the stacked film of aluminium is about 0.03mm, and average particulate diameter is 100 μ m.The resin that the reinforcement aluminium lamination is used has used polypropylene.Melt to connect by heat stacked film is sealed, thus process vessel.

Then, the strip-shaped positive electrode terminal is electrically connected on the positive pole, the negative terminal with band shape is electrically connected on the negative pole simultaneously.The spacer that will be made of the polyethylene system multiple aperture plasma membrane ofthickness 12 μ m covers on the positive pole with connecting airtight.Negative pole is overlapped onto with making it relative on the covered positive pole of spacer.They are wound up as spirality, produce electrode group.To this electrode group formation flat of pressurizeing.The electrode group that forms flat is inserted in the container.

Make the LiBF of lithium salts₄With 1.5mo1/L be mixed into volume ratio (EC: GBL) 1: 2 mixed in the organic solvent of EC and GBL, modulate aqueous nonaqueous electrolyte.Resulting nonaqueous electrolyte is injected in the container, produce have above-mentioned structure shown in Figure 2 and thickness 6.5mm, width 70mm, the slim non-aqueous electrolyte battery of height 100mm.Battery weight is 90g, and the metric system capacity is 3000mAh.

3 these thin lithium ion storage batterys are connected in series on the positive plate, become a module.28 these modules that are connected in series being produced the battery pack of regeneration with accumulating system.Use this battery pack, battery control unit (BMU), boosting unit, produce above-mentioned regeneration accumulating system shown in Figure 1.

Regeneration is placed under 55 ℃ the environment with accumulating system,, with regenerative current (input) battery is charged simultaneously from DC motor with the surface temperature of temperature sensor monitors battery.Because battery temperature is 60 ℃,, make the maximum of charged state (SOC (State Of Charge) will be full of electric state till rated capacity as 100%) become 85% so calculate charging capacity automatically by BMU.Carry out the metering of voltage on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.65V (closed circuit), is equivalent to 0.946 * V0 (V).In addition, when being full of electricity under 25 ℃, the maximum charge final voltage V0 in the end of charge voltage of the unit cell of a module of formation is 2.8 (V).Under this temperature environment, carry out the cyclic test of input and output.

(embodiment 2)

Regeneration is placed under 75 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.Because battery temperature is 80 ℃, so calculate charging capacity automatically by BMU, makes the maximum of SOC become 65%.Carry out the metering of voltage on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.45V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(embodiment 3)

Regeneration is placed under 40 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.Because battery temperature is 45 ℃, so calculate charging capacity automatically by BMU, makes the maximum of SOC become 90%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.68V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(embodiment 4)

Regeneration is placed under 65 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.Because battery temperature is 70 ℃, so calculate charging capacity automatically by BMU, makes the maximum of SOC become 70%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.50V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(embodiment 5)

Regeneration is placed under 50 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.Because battery temperature is 55 ℃, so calculate charging capacity automatically by BMU, makes the maximum of SOC become 88%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.66V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(embodiment 6)

Regeneration is placed under 45 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.Because battery temperature is 65 ℃, so calculate charging capacity automatically by BMU, makes the maximum of SOC become 85%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.38V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(comparative example 1)

Regeneration is placed under 55 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.At battery temperature is under 60 ℃, calculates charging capacity automatically by BMU, makes the maximum of SOC become 105%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, the maximum charge final voltage is 2.80V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(comparative example 2)

Regeneration is placed under 75 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.At battery temperature is under 80 ℃, calculates charging capacity automatically by BMU, makes the maximum of SOC become 110%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, the maximum charge final voltage is 2.80V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(comparative example 3)

Regeneration is placed under 40 ℃ the environment with accumulating system, and the surface temperature of monitoring battery is charged to battery with the regenerative current (input) from DC motor simultaneously.At battery temperature is under 45 ℃, calculates charging capacity automatically by BMU, makes the maximum of SOC become 102%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, the maximum charge final voltage is 2.80V (closed circuit).In addition, except carrying out under this temperature environment the cyclic test of input and output, be the regeneration accumulating system the same with embodiment 1.

(comparative example 4)

In negative electrode active material uses pressure surface spacing (the metho face pitch) based carbon fiber, be the regeneration accumulating system the same with embodiment 1.

(comparative example 5)

In negative electrode active material uses the pressure surface spacing based carbon fiber, be the regeneration accumulating system the same with comparative example 1.

At the regeneration accumulating system of resulting embodiment 1～6 and comparative example 1～5, implement following input and output cyclic test.After till SOC20%, having carried out exporting (constant current 5C speed), import (maximum 10C speed) with regenerated electric power from DC motor, till each maximum charge final voltage V1, charge, become each SOC value of regulation.These input and output are carried out in circulation, the output density (10 second) under the charged state of the SOC50% after measurement 1000 circulations, the expansion rate (thickness with the unit cell before the cyclic test is benchmark) of unit cell.Sum up its value and be table 1.In addition, in table 1, put down in writing simultaneously under maximum charge final voltage V1 and 25 ℃ be full of electricity the time the relation of maximum charge final voltage V0.

Table 1

According to the result of table 1 as can be known, the regeneration storage battery system of embodiment 1～6 is compared with comparative example 1～3, has kept high output density under more than or equal to 45 ℃ battery temperature, has suppressed the expansion of unit cell simultaneously.In the regeneration storage battery system of theembodiment 1,3,5 that satisfies 0.9 * V0≤V1≤0.96 * V0, output density and unit cell thickness increment rate both sides after 1000 circulations are very superior especially.

In the regeneration storage battery system of comparative example 4,5, used the carbon material as negative electrode active material.Therefore, have more than and be maximum charge final voltage V1, gas generated also many, the unit cell thickness increment rate after 1000 circulations becomes big, and output density reduces.

(embodiment 7)

The negative pole manufacture method is described.Make spinel type lithium titanate (Li as the average particulate diameter 0.9 μ m of active material₄Ti₅O₁₂), as the carbon dust of the average particulate diameter 0.4 μ m of conductive agent, to become weight ratio as the polyfluoro acetylene fork (PVdF) of bonding agent be like that to cooperate at 90: 7: 3, and be distributed in n-methyl pyrrolidone (NMP) solvent, after modulating paste, (purity is 99.4% to be applied to thickness and to be the alloy foil of average particulate diameter 50 μ m of 12 μ m, contain 5%Si and Fe), dry also through the pressurization operation, produce electrode density 2.4g/cm³Negative pole.In addition, form negative electrode active material layer on the two sides of negative electrode collector, the aggregate thickness of negative electrode active material layer is 60 μ m.In addition, the thickness of the negative electrode active material layer of negative electrode collector one side is 30 μ m.

Anodal manufacture method is described.As positive active material, prepare the lithium nickel cobalt manganese composite oxides (LiNi of average particulate diameter 1 μ m_1/3Co_1/3Mn_1/3O₂), wherein as electric conducting material with respect to the powdered graphite of all cooperation ofpositive pole 8 weight %, as bonding agent with respect to all PVdF that cooperates 5 weight % of positive pole, and be distributed in n-methyl pyrrolidone (NMP) solvent, modulate paste.Paste is applied to the two sides of the alloy foil that thickness is theaverage particulate diameter 12 μ m of 15 μ m (purity is 99.4%, contains 0.5% Si and Fe), dry and through the pressurization operation, produce electrode density 3.5g/cm³Positive pole.In addition, form positive electrode active material layer on the two sides of positive electrode collector, the aggregate thickness of positive electrode active material layer is 60 μ m.In addition, the thickness of the positive electrode active material layer of positive electrode collector one side is 30 μ m.

Container use with embodiment 1 in the same stacked film that contains aluminium.

Then, the strip-shaped positive electrode terminal is electrically connected on the positive pole, the negative terminal with band shape is electrically connected on the negative pole simultaneously.The spacer that will be made of the polyethylene system multiple aperture plasma membrane ofthickness 12 μ m covers on the positive pole with connecting airtight.Negative pole is overlapped onto with making it relative on the covered positive pole of spacer.They are wound up as spirality, produce electrode group.To this electrode group formation flat of pressurizeing.The electrode group that forms flat is inserted in the container.

Make the LiBF of lithium salts₄With 1.5mol/L be dissolved into volume ratio (EC: GBL) 1: 2 mixed in the organic solvent of EC and GBL, modulate aqueous nonaqueous electrolyte.Resulting nonaqueous electrolyte is injected in the container, produce have above-mentioned structure shown in Figure 2 and rated capacity 6Ah, thickness 4mm, the platypelloid type non-aqueous electrolyte battery of width 100mm, height 170mm.

Behind 10 the resulting storage batterys that have been connected in series, with splicing tape it is become one, obtain battery pack.Use this battery pack to make the battery component of the structure shown in above-mentioned Fig. 5,6, obtain battery system.In addition, to the outermost storage battery in both sides that constitutes battery pack, the storage battery that constitutes the intermediate layer, carry out the temperature measuring of thermistor.

Accumulating system is placed under 45 ℃ the environment,, charges rapidly with the speed of 20C simultaneously with the temperature of thermistor monitor battery pack.Because battery temperature is 60 ℃, so calculate charging capacity automatically byprotective circuit 26, makes the maximum of SOC become 80%.Carry out voltage measurement on one side, to target charging capacity till charge on one side.During end of charge voltage in the closed circuit of the unit cell that relatively constitutes a module, maximum charge final voltage V1 is 2.55V (closed circuit), is equivalent to 0.85 * V0 (V).Maximum charge final voltage V0 when in addition, being full of electricity under 25 ℃ is 3.0 (V).Under this temperature environment, carry out the cyclic test of input and output.Below put down in writing the condition of cyclic test.

After having carried out exporting (constant current 5C speed) till the SOC20%, import, till the SOC value of regulation and maximum charge final voltage V1, charge with 20C speed.These input and output are carried out in circulation, the output density (10 second) under the charged state of the SOC50% after measurement 1000 circulations, the expansion rate of unit cell.In addition, the thickness of the unit cell of the expansion rate of unit cell before with cyclic test is benchmark.

Consequently: the expansion rate of the unit cell after 1000 circulations is that the output density after 1.0%, 1000 circulation is 1500W/kg (10 second).

In addition, the present invention has more than and is limited to the foregoing description, the implementation phase, in the scope that does not break away from its aim, can and specialize inscape distortion.In addition, a plurality of structural elements that disclosed by suitably making up the foregoing description can form various inventions.For example, can from the entire infrastructure key element shown in the embodiment, delete several structural elements.And then, also can suitably make up the structural element among the different embodiment.In addition, input and output speed has more than and is limited to above-mentioned speed, can be set to the interior value arbitrarily of scope of 2C～120C.In addition, input and output can be carried out continuously, also input and output can be carried out pulsedly.Burst length can be 0.1 second～30 seconds scope.

Claims (18)

Translated fromChinese

1.一种蓄电系统，其特征在于包括：1. A power storage system, characterized in that it comprises:具备由非水电解质蓄电池构成的单位单元的电池组，该非水电解质蓄电池具备包含锂钛复合氧化物的负极层、包含载置上述负极层的集电体的负极、正极和非水电解质；A battery pack comprising a unit cell composed of a nonaqueous electrolyte storage battery having a negative electrode layer comprising a lithium-titanium composite oxide, a negative electrode comprising a current collector on which the negative electrode layer is placed, a positive electrode, and a nonaqueous electrolyte;用于测定上述电池组的温度的温度传感器；a temperature sensor for determining the temperature of the aforementioned battery pack;用于测量上述单位单元的电压的电压计；a voltmeter for measuring the voltage of the above unit cell;在上述电池组的温度大于等于45℃小于等于90℃时，将上述单位单元的最大充电终止电压V₁控制在下式(1)的范围内的充电控制装置，When the temperature of the above-mentioned battery pack is greater than or equal to 45°C and less than or equal to 90°C, a charge control device that controls the maximum charge termination voltage_V1 of the above-mentioned unit cells within the range of the following formula (1),0.85×V₀≤V₁≤0.96×V₀(1)0.85×V₀ ≤V₁ ≤0.96×V₀ (1)其中，V₀表示在25℃将上述电池组充满电时的上述单位单元的最大充电终止电压，其中上述V₀、V₁的单位是V。Wherein, V₀ represents the maximum end-of-charge voltage of the above-mentioned unit cells when the above-mentioned battery pack is fully charged at 25° C., wherein the units of the above-mentioned V₀ and V₁ are V.2.根据权利要求1所述的蓄电系统，其特征在于：2. The power storage system according to claim 1, characterized in that:上述负极的集电体由铝箔或铝合金箔形成。The current collector of the negative electrode is formed of aluminum foil or aluminum alloy foil.3.根据权利要求1所述的蓄电系统，其特征在于：3. The power storage system according to claim 1, characterized in that:上述非水电解质蓄电池各自具有2C～120C的输入输出速率。The non-aqueous electrolyte secondary batteries each have an input/output rate of 2C to 120C.4.根据权利要求1所述的蓄电系统，其特征在于：4. The power storage system according to claim 1, characterized in that:上述锂钛复合氧化物的粉末颗粒的平均颗粒直径小于等于1μm。The average particle diameter of the powder particles of the lithium-titanium composite oxide is less than or equal to 1 μm.5.根据权利要求1所述的蓄电系统，其特征在于：5. The power storage system according to claim 1, characterized in that:上述充电控制装置在上述电池组的温度大于等于45℃小于等于60℃时，将上述单位单元的最大充电终止电压V₁控制为上述式(1)的范围内。The charge control device controls the maximum end-of-charge voltage V₁ of the unit cell to be within the range of the above formula (1) when the temperature of the battery pack is 45° C. or higher and 60° C. or lower.6.根据权利要求1所述的蓄电系统，其特征在于：6. The power storage system according to claim 1, characterized in that:上述锂钛复合氧化物的粉末颗粒包含尖晶石型锂钛粉末颗粒。The powder particles of the lithium-titanium composite oxide described above include spinel-type lithium-titanium powder particles.7.根据权利要求1所述的蓄电系统，其特征在于：7. The power storage system according to claim 1, characterized in that:上述正极包含用Li_aNi_bCo_cMn_dO₂表示的锂镍钴锰复合氧化物，其中表示该元素的摩尔数相对于化合物的总摩尔数的比的摩尔比a、b、c和d为0≤a≤1.1、b+c+d＝1。The above-mentioned positive electrode comprises a lithium nickel cobalt manganese composite oxide represented by Li_a Ni_b Co_c Mn_d O₂ , wherein the molar ratios a, b, c and d representing the ratio of the number of moles of the element to the total number of moles of the compound 0≤a≤1.1, b+c+d=1.8.根据权利要求1所述的蓄电系统，其特征在于：8. The power storage system according to claim 1, characterized in that:上述非水电解质包含从由γ-丁内酯、丙撑碳酸酯、乙烯碳酸酯构成的组内选择出的至少一种溶剂。The non-aqueous electrolyte contains at least one solvent selected from the group consisting of γ-butyrolactone, propylene carbonate, and ethylene carbonate.9.根据权利要求1所述的蓄电系统，其特征在于：9. The power storage system according to claim 1, characterized in that:在上述电池组的温度大于等于45℃小于等于90℃时，上述非水电解质蓄电池的最大充电终止电压V₁为下式(2)的范围内，When the temperature of the above-mentioned battery pack is greater than or equal to 45°C and less than or equal to 90°C, the maximum end-of-charge voltage_V of the above-mentioned non-aqueous electrolyte storage battery is in the range of the following formula (2),0.9×V₀≤V₁≤0.96×V₀(2)0.9×V₀ ≤V₁ ≤0.96×V₀ (2)其中，V₀表示在25℃将上述电池组充满电时的上述单位单元的最大充电终止电压。Here, V₀ represents the maximum end-of-charge voltage of the unit cell when the battery pack is fully charged at 25°C.10.一种再生蓄电系统，其特征在于包括：10. A regenerative power storage system, characterized by comprising:以非水电解质蓄电池为单位单元的电池组，该非水电解质蓄电池具备包含锂钛复合氧化物的负极层、包含载置上述负极层的集电体的负极；A battery pack using a non-aqueous electrolyte storage battery as a unit cell, the non-aqueous electrolyte storage battery having a negative electrode layer comprising a lithium-titanium composite oxide, and a negative electrode comprising a current collector on which the negative electrode layer is placed;用于发出对上述电池组进行充电的再生电力的发电机；A generator for generating regenerative electricity for charging the battery;在上述电池组的温度大于等于45℃小于等于90℃时，将上述单位单元的最大充电终止电压V₁控制在下式(1)的范围内的充电控制装置，When the temperature of the above-mentioned battery pack is greater than or equal to 45°C and less than or equal to 90°C, a charge control device that controls the maximum charge termination voltage_V1 of the above-mentioned unit cells within the range of the following formula (1),0.85×V₀≤V₁≤0.96×V₀(1)0.85×V₀ ≤V₁ ≤0.96×V₀ (1)其中，V₀表示在25℃将上述电池组充满电时的上述单位单元的最大充电终止电压，其中上述V₀、V₁的单位是V。Wherein, V₀ represents the maximum end-of-charge voltage of the above-mentioned unit cells when the above-mentioned battery pack is fully charged at 25° C., wherein the units of the above-mentioned V₀ and V₁ are V.11.根据权利要求10所述的再生蓄电系统，其特征在于：11. The regenerative power storage system according to claim 10, characterized in that:上述负极的集电体由铝箔或铝合金箔形成。The current collector of the negative electrode is formed of aluminum foil or aluminum alloy foil.12.根据权利要求10所述的再生蓄电系统，其特征在于：12. The regenerative power storage system according to claim 10, characterized in that:上述非水电解质蓄电池各自具有2C～120C的输入输出速率。The non-aqueous electrolyte secondary batteries each have an input/output rate of 2C to 120C.13.根据权利要求10所述的再生蓄电系统，其特征在于：13. The regenerative power storage system according to claim 10, characterized in that:上述锂钛复合氧化物的粉末颗粒的平均颗粒直径小于等于1μm。The average particle diameter of the powder particles of the lithium-titanium composite oxide is less than or equal to 1 μm.14.根据权利要求10所述的再生蓄电系统，其特征在于：14. The regenerative power storage system according to claim 10, characterized in that:上述充电控制装置在上述电池组的温度大于等于45℃小于等于60℃时，将上述单位单元的最大充电终止电压V₁控制为上述式(1)的范围内。The charge control device controls the maximum end-of-charge voltage V₁ of the unit cell to be within the range of the above formula (1) when the temperature of the battery pack is 45° C. or higher and 60° C. or lower.15.根据权利要求10所述的再生蓄电系统，其特征在于：15. The regenerative power storage system according to claim 10, characterized in that:上述锂钛复合氧化物的粉末颗粒包含尖晶石型锂钛粉末颗粒。The powder particles of the lithium-titanium composite oxide described above include spinel-type lithium-titanium powder particles.16.根据权利要求10所述的再生蓄电系统，其特征在于：16. The regenerative power storage system according to claim 10, characterized in that:上述正极包含用Li_aNi_bCo_cMn_dO₂表示的锂镍钴锰复合氧化物，其中表示该元素的摩尔数相对于化合物的总摩尔数的比的摩尔比a、b、c和d为0≤a≤1.1、b+c+d＝1。The above-mentioned positive electrode comprises a lithium nickel cobalt manganese composite oxide represented by Li_a Ni_b Co_c Mn_d O₂ , wherein the molar ratios a, b, c and d representing the ratio of the number of moles of the element to the total number of moles of the compound 0≤a≤1.1, b+c+d=1.17.根据权利要求10所述的再生蓄电系统，其特征在于：17. The regenerative power storage system according to claim 10, characterized in that:在上述电池组的温度大于等于45℃小于等于90℃时，上述非水电解质蓄电池的最大充电终止电压V₁为下式(2)的范围内，When the temperature of the above-mentioned battery pack is greater than or equal to 45°C and less than or equal to 90°C, the maximum end-of-charge voltage_V of the above-mentioned non-aqueous electrolyte storage battery is in the range of the following formula (2),0.9×V₀≤V₁≤0.96×V₀(2)0.9×V₀ ≤V₁ ≤0.96×V₀ (2)其中，V₀表示在25℃将上述电池组充满电时的上述单位单元的最大充电终止电压。Here, V₀ represents the maximum end-of-charge voltage of the unit cell when the battery pack is fully charged at 25°C.18.一种汽车，其特征在于：具备权利要求10记载的再生蓄电系统。18. An automobile comprising the regenerative power storage system according to claim 10.

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