CN101071853A - Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method - Google Patents

Abstract

Translated fromChinese

本发明公开一种用于电池或电化学容器负极材料的纳米钛酸锂、其与二氧化钛的复合物的制备方法，包括以下步骤：(1)含钛化合物与氢氧化钠(钾)加热反应，冷却，水洗涤至不同的pH值，干燥得钛酸钠(钾)或钛酸－钛酸钠(钾)复合物；(2)将步骤(1)的产物与无机锂盐混合，加热至451～1000℃下熔融交换反应30分钟～48小时，或者将步骤(1)的产物在惰性气体或还原性气体下，与有机锂盐或者有机锂盐和无机锂盐的混合物混合，加热至150～1000℃熔融交换反应30分钟～48小时，然后水洗涤，干燥得最终产物。本发明用于电池或电化学容器负极材料的制造，产品结晶性能好、电化学性能优异、工艺简单、易于工业化生产。

The invention discloses a method for preparing nano-lithium titanate and a composite thereof with titanium dioxide used as negative electrode materials for batteries or electrochemical containers, comprising the following steps: (1) heating and reacting titanium-containing compounds with sodium (potassium) hydroxide, Cool, wash with water to different pH values, and dry to obtain sodium titanate (potassium) or titanate-sodium titanate (potassium) complex; (2) Mix the product of step (1) with inorganic lithium salt and heat to 451 Melt exchange reaction at ~1000°C for 30 minutes to 48 hours, or mix the product of step (1) with organic lithium salt or a mixture of organic lithium salt and inorganic lithium salt under inert gas or reducing gas, and heat to 150 ~ Melt exchange reaction at 1000°C for 30 minutes to 48 hours, then washed with water and dried to obtain the final product. The invention is used in the manufacture of battery or electrochemical container negative electrode materials, and the product has good crystallization performance, excellent electrochemical performance, simple process and easy industrial production.

Description

The preparation method of compound who is used for nano lithium titanate, itself and the titanium dioxide of battery or electrochemical vessel negative material

Technical field

The invention belongs to technical field of nano material, relate to the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide.

Background technology

Present commercial lithium ion battery negative material adopts various embedding lithium material with carbon elements mostly, there are some shortcomings in material with carbon element as lithium ion battery negative material: the one, and the current potential of material with carbon element and the current potential of lithium metal are very approaching, when over-charging of battery, lithium metal may be separated out and forms Li dendrite in carbon electrodes, thereby causes short circuit; The 2nd, first charge-discharge efficiency is low; The 3rd, have an effect with electrolyte; The 4th, there is tangible voltage delay phenomenon; The 5th, material with carbon element preparation method more complicated; The 6th, though the alloy type negative material generally has higher specific capacity, the embedding repeatedly of lithium is taken off and is caused the change in volume of alloy type negative pole in charge and discharge process bigger, and efflorescence was lost efficacy gradually, thereby cycle performance is relatively poor.Along with the rise of environmental-protecting type electric automotive research, electrochemical vessel has become another research focus behind lithium ion battery as a kind of energy storage device with high power density.It and secondary cell combination are used, can satisfy preferably that electric automobile starts, quickens, during climbing to high-power requirement, and reclaim the transient energy that electric automobile when brake produces rapidly, make secondary cell maintain work under the more stable current status all the time, prolong its cycle life.

Lithium titanate is that a kind of lithium inserts the zero strain material, and as lithium ion battery negative material not recurring structure change in charge and discharge process, good cycle has good charge and discharge platform; Do not react with electrolyte; Low price, preparation is compared with commercial carbon negative pole material easily, has better chemical property and fail safe usually.Can also be used to replace a utmost point of active carbon double electric layer capacitor, bring into play the advantage of its relative height ratio capacity; The big order of magnitude of its chemical diffusion coefficient ratio carbon electrode material becomes desirable hybrid electrochemical capacitor negative material simultaneously.

The synthetic method of lithium titanate adopts high-temperature solid phase reaction method and sol-gel process mostly at present.The high temperature solid-state synthesis technique of lithium titanate is similar to other composite oxide of metal, usually with TiO₂And LiOH (or LiCO₃) be raw material, by high temperature (800-1000 ℃), for a long time heat treatment forms product, and the shortcoming of this method is the energy consumption height, and product mostly is micron or submicron particles greatly, and big particle size is unfavorable for the quick embedding of lithium ion and deviates from.

Advantages such as sol-gel process is because to have a synthesis temperature low, and particle size is little, and homogeneity is good, and specific area is big and being widely adopted gradually.But sol-gel process need use expensive organic alkoxide as presoma, and complex process, therefore is difficult to realize that large-scale industrial production satisfies the wilderness demand of energy field.

Summary of the invention

The purpose of this invention is to provide that a kind of product crystal property is good, chemical property is excellent, technology is simple, be easy to the nano lithium titanate that is used for battery or electrochemical vessel negative material of suitability for industrialized production, the preparation method of itself and titanium dioxide compound.

The present invention realizes above-mentioned purpose by the following technical solutions: the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide may further comprise the steps:

(1), titanium-containing compound and NaOH or potassium hydroxide adds thermal response, reaction back mixed liquor cooling-sedimentation, water washing is to different pH values, dry nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps dry nanometer potasium titanate or the metatitanic acid-potassium titanate compound of getting;

(2), the product of step (1) is mixed with inorganic lithium salt, be heated to 451～1000 ℃ of following fusion exchange reactions 30 minutes～48 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound;

Another kind method is that product with step (1) is under inert atmosphere or reducing atmosphere, mix with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions 30 minutes～48 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.

Inert gas is selected nitrogen or argon gas, and reducibility gas is selected hydrogen.

The method of the preferred following steps of above-mentioned preparation method: the product and the inorganic lithium salt of step (1) were mixed and heated to 451～700 ℃ of followingfusion exchange reactions 2～12 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.

Above-mentioned preparation method is the method for following steps preferably: under inert gas or reducibility gas, the product of step (1) is mixed with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 250～600 ℃ offusion exchange reactions 2～12 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.

In the step (1), the reaction after washing wash to the pH value be 6～12, step (2) product is lithium titanate-titanium dioxide compound.

In the step (1), the reaction after washing wash to the pH value greater than 12.5, step (2) product is a lithium titanate.

The mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.

Described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.

The preparation method of nano barium titanate sodium (potassium) or metatitanic acid-sodium titanate (potassium) presoma:

Titanium-containing compound is mixed in container with NaOH or the potassium hydroxide aqueous solution of percentage by weight 20-80%, with mode reflux such as hydro-thermal reaction in routine heating, microwave heating or the autoclave pressure 30 minutes to 72 hours; Reaction back mixed liquor cooling-sedimentation, and control washing degree get nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps get nanometer potasium titanate or metatitanic acid-potassium titanate compound;

It is presoma that the present invention adopts the sodium titanate of one-dimensional nano structure or metatitanic acid-sodium titanate nanotubes, potassium titanate or metatitanic acid-Nano lines of potassium titanate compound, by control washing degree, presoma is washed different pH values, regulate the ratio of titanate and metatitanic acid in the presoma, and then the ratio of lithium titanate and titanium dioxide in the control end product.As lithium ion battery material, lithium titanate has good cyclical stability, but its theoretical specific capacity is lower; Titanium dioxide is compared with lithium titanate has higher theoretical specific capacity, by controlling the two content to suitable ratio, can make product both have cyclical stability preferably, has higher specific capacity again.In addition, metatitanic acid-titanate of the present invention and inorganic lithium salt are mixed and heated to 451～1000 ℃ of following fusion exchange reactions, perhaps nano barium titanate-titanate compound mixes with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions, these two kinds of reactions are to carry out the fusion exchange under higher temperature, hot conditions helps obtaining the better lithium titanate of crystal property, has good stability as negative material, have long useful life, and shortened the reaction time.Reaction raw materials is except selecting inorganic lithium salt, also select to use organic lithium salt, when organic lithium salt carries out the fusion exchange, in inert atmosphere (as nitrogen, argon gas) or reducing atmosphere (as hydrogen) organic substance generation carbonization down, be coated on the lithium titanate surface, improve the conductivity of lithium titanate, improved the performance of battery.Nano lithium titanate, the lithium titanate-titanium dioxide compound of the present invention's preparation have showed excellent chemical property as electrochemical energy storage materials, lithium titanate-titanium dioxide compound charge-discharge test shows that the simulated battery specific discharge capacity reaches 171mAh/g, near theoretical value 175mAh/g, discharge platform is near 1.6～1.8; The nano lithium titanate charge-discharge test shows that the simulated battery first discharge specific capacity reaches 160mAh/g, and discharge platform all has charge and discharge cycles stability preferably near 1.5V.In new type lithium ion battery and electrochemical capacitor, have wide practical use.

Method of the present invention is raw materials used cheap and easy to get, and is simple to operate, productive rate height, easy realization of large-scale production.

Description of drawings

Fig. 1 is the Electronic Speculum figure of embodiment 1 lithium titanate;

Fig. 2 is the Electronic Speculum figure ofembodiment 2 lithium titanates-titanium dioxide compound;

Fig. 3 is the X-ray diffractogram thatembodiment 2 lithium titanates, titanium dioxide mix phase;

Fig. 4 is the X-ray diffractogram ofembodiment 4 pure phase lithium titanates;

Fig. 5 is the charging and discharging curve of four circulations of compound of nano lithium titanate-titanium dioxide;

Fig. 6 is the charging and discharging curve of four circulations of nano lithium titanate.

The used instrument of tem analysis is the JEM-100CX II type transmission electron microscope (TEM) of NEC (JEOL), and accelerating voltage is 100kV, and sample preparation is adopted the ultrasonic dispersion of absolute ethyl alcohol back to drip and born on the copper mesh of carbon film air drying.

The used instrument of XRD analysis is X ' pert pro type x-ray diffractometer (XRD, Holland Philips company), adopt CuK α line excitaton source, λ=0.15418366nm, voltage 40kV, electric current 40mA, sample can be powder and place pressing of sample stage groove or sample dispersion to drip on slide in acetone, dry the back and become film, directly detect.

The used instrument of charge-discharge test is the Land battery test system that the blue electric Electronics Co., Ltd. in Wuhan produces, and model is CT2001A, carries out the 0.2C multiplying power and carry out electro-chemical test in 0.8～2.6V scope.

Embodiment

Embodiment 1, gets 3g TiO₂Slowly add and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 3mol/L, the control temperature is 120 ℃, stirs and adds the backflow condenser pipe, reacts 24 hours, get the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 13 to pH, suction filtration, drying then, and then and 12g lithium nitrate mixed grinding, and added heat exchange 2.5 hours in 500 ℃ of following fusions, wash dry spinel lithium titanate product; As shown in Figure 1, the diameter of nano lithium titanate is approximately 8～10nm, and length is about 100nm.

Embodiment 2, get metatitanic acid 10g (industrial slurry, weight content 44.04%, benefit reaches Fine Chemical Co., Ltd and produces), slowly add and fill in the polytetrafluoroethylene reaction vessel of KOH solution that 100ml concentration is 10mol/L, place microwave oven, low fire in being set to (750W, work 10s stops 12s), mechanical agitation, add the backflow condenser pipe, reaction behind the 6h diameter be the Nano lines of potassium titanate of several nanometers, wash to pH be 7 and dry, get 25g lithium citrate and lithium chloride mixture (weight ratio is 1: 3) and dried potassium titanate/metatitanic acid composite fibre mixed grinding then, and placing sintering furnace, under the nitrogen protection, 1000 ℃ of fusions add heat exchange 2h, get lithium titanate-titanium dioxide compound, its pattern as shown in Figure 2; Crystal structure as shown in Figure 3, it comprises two kinds of different crystal forms materials: the Li of cubic spinel structure₄Ti₅O₁₂With anatase structured TiO₂

Embodiment 3, get 3g TiO₂, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 6 to pH, suction filtration, drying then; And then and the mixture of the lithium hydroxide of 5g and lithium nitrate (weight ratio is 1: 5) grind, and add heat exchange 48h in 451 ℃ of following fusions, wash dry must the product spinel lithium titanate and the compound of titanium dioxide.

Embodiment 4, get 3g TiO₂Slowly add and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L; get the nanotube sodium titanate behind the microwave heating 5h; centrifugal sedimentation and to wash to pH be that filter 13 backs; with this pastel and 10g lithium benzoate mixed grinding; under the hydrogen shield, behind 370 ℃ of following heat exchange 5h, get product.XRD result shows that product is the lithium titanate of pure phase as shown in Figure 4.

Embodiment 5; get metatitanic acid 10g (industrial slurry; weight content 44.04%; benefit reaches Fine Chemical Co., Ltd and produces); slowly add and fill in the polytetrafluoroethylene reaction vessel of KOH solution that 100ml concentration is 10mol/L; place microwave oven; low fire in being set to (750W, work 10s stops 12s); mechanical agitation; add the backflow condenser pipe, reaction behind the 6h diameter be the Nano lines of potassium titanate of several nanometers, wash to pH be 7.5; and it is dry; get 20g lithium citrate and lithium chloride mixture (weight ratio is 1: 3) and dried potassium titanate/metatitanic acid composite fibre mixed grinding then, and place sintering furnace, under the nitrogen protection; 600 ℃ of fusions add heat exchange 8h, get lithium titanate-titanium dioxide compound.

Embodiment 6, get 3g TiO₂Slowly add and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L; get the nanotube sodium titanate behind the microwave heating 5h; centrifugal sedimentation and to wash to pH be that filter 13 backs; with this pastel and 4g lithium benzoate mixed grinding; under the argon shield, and behind 250 ℃ of following heat exchange 12h, get the nanotube-shaped lithium titanate of product.

Embodiment 7, get the 3g metatitanic acid; slowly add and fill in the polytetrafluoroethylcontainer container of KOH solution that 300ml concentration is 10mol/L; get the nano wire potassium titanate behind the microwave heating 5h; centrifugal sedimentation and to wash to pH be that filter 13 backs; with this pastel and 4g lithium acetate mixed grinding; under the nitrogen protection, and, get the nanometer fibrous lithium titanate of product after the washing in 150 ℃ of following heat exchange 48h.

Embodiment 8, get metatitanic acid 10g, slowly add and fill in the polytetrafluoroethylene reaction vessel of NaOH solution that 100ml concentration is 10mol/L, place microwave oven, low fire (750W in being set to, work 10s, stop 12s), mechanical agitation adds the backflow condenser pipe, reaction behind the 6h sodium titanate nanotubes, wash to pH be 13; Get the mixture (weight ratio is 1: 5: 5) and the dried presoma mixed grinding of 20g acrylic acid lithium, lithium chloride and lithium sulfate, and place sintering furnace, under the nitrogen protection, 1000 ℃ of fusions add heat exchange 30min, get the product lithium titanate.

Embodiment 9, get 3g TiO₂, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 12 to pH, suction filtration, drying then; And then and the lithium bromide of 5g grind, and add heat exchange 2h in 700 ℃ of following fusions, wash dry must the product spinel lithium titanate and the compound of titanium dioxide.

Embodiment 10, get 3g TiO₂, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 8 to pH, suction filtration, drying then; And then and the lithium phosphate of 5g grind, and add heat exchange 30min in 1000 ℃ of following fusions, wash dry must the product spinel lithium titanate and the compound of titanium dioxide.

Embodiment 11, get 3g TiO₂, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 13 to pH, suction filtration, drying then; And then and the lithium hydroxide of 5g grind, and add heat exchange 12h in 600 ℃ of following fusions, wash dry must the product spinel lithium titanate.

The chemical property of the nano lithium titanate ofembodiment 2 preparations---constant current charge-discharge test:

Utilize the mixed of the black and bonding agent Kynoar (PVDF) of nano lithium titanate-titanium dioxide compound, the conductive acetylene ofembodiment 2 preparation according toweight ratio 80%: 10-12%: 8-10%, with N-methyl-pyrrolidones (NMP) is solvent, fully stirring becomes pastel even, good fluidity, be coated on equably then on the Copper Foil collector, form electrode diaphragm.Be placed in the electric heating constant temperature air dry oven pole piece that coats following dry 12 hours at 110 ℃.As negative pole, use 1mol/L LiPF with metal lithium sheet₆/ (EC+DMC) be electrolyte, electrode diaphragm is assembled into simulated battery for anodal in the glove box that is full of Ar gas, carry out the constant current charge-discharge test then on the LAND test macro.As can be seen from Figure 5 this simulated battery first discharge specific capacity reaches 171mAh/g, and near theoretical value 175mAh/g, discharge platform and has charge and discharge cycles stability preferably near 1.6～1.8.

The chemical property of the nano lithium titanate of embodiment 8 preparations---constant current charge-discharge test:

Black and bonding agent Kynoar (PVDF) is according to the mixed ofweight ratio 80%: 10-12%: 8-10% with nano lithium titanate, the conductive acetylene of embodiment 8 preparation, with N-methyl-pyrrolidones (NMP) is solvent, fully stirring becomes pastel even, good fluidity, be coated on equably then on the Copper Foil collector, form electrode diaphragm.Be placed in the electric heating constant temperature air dry oven pole piece that coats following dry 12 hours at 110 ℃.As negative pole, use 1mol/L LiPF with metal lithium sheet₆/ (EC+DMC) be electrolyte, electrode diaphragm is assembled into simulated battery for anodal in the glove box that is full of Ar gas, carry out the constant current charge-discharge test then on the LAND test macro.As can be seen from Figure 6 this simulated battery first discharge specific capacity reaches 160mAh/g, and discharge platform has discharge platform and charge and discharge cycles stability preferably preferably near 1.5V.

Claims (9)

1, the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide is characterized in that, may further comprise the steps:

(1), titanium-containing compound and NaOH or potassium hydroxide adds thermal response, reaction back mixed liquor cooling-sedimentation, water washing is to different pH values, dry nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps dry nanometer potasium titanate or the metatitanic acid-potassium titanate compound of getting;

(2), the product of step (1) is mixed with inorganic lithium salt, be heated to 451～1000 ℃ of following fusion exchange reactions 30 minutes～48 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide; Perhaps with the product of step (1) under inert gas or reducibility gas, mix with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions 30 minutes～48 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.

2, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 1, itself and titanium dioxide, it is characterized in that, the product and the inorganic lithium salt of step (1) were mixed and heated to 451～700 ℃ of following fusion exchange reactions 2～12 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.

3, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 1, itself and titanium dioxide, it is characterized in that, under inert gas or reducibility gas, the product of step (1) is mixed with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 250～600 ℃ of fusion exchange reactions 2～12 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.

4, as the preparation method of the compound of any described nano lithium titanate that is used for battery or electrochemical vessel negative material of claim 1～3, itself and titanium dioxide, it is characterized in that, in the step (1), the reaction after washing wash to the pH value be 6～12, step (2) product is lithium titanate-titanium dioxide compound.

5, as the preparation method of the compound of any described nano lithium titanate that is used for battery or electrochemical vessel negative material of claim 1～3, itself and titanium dioxide, it is characterized in that, in the step (1), the reaction after washing wash to the pH value greater than 12.5, step (2) product is a lithium titanate.

6, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 4, itself and titanium dioxide, it is characterized in that the mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.

7, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 5, itself and titanium dioxide, it is characterized in that the mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.

8, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 6, itself and titanium dioxide, it is characterized in that described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.

9, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 7, itself and titanium dioxide, it is characterized in that described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.

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