Invention content
The purpose of the present invention includes providing a kind of preparation method of nickel-cobalt lithium manganate cathode material, is prepared using wet method, shouldMethod not only can effectively solve the uniform sex chromosome mosaicism of raw material mixing, can also simplify technical operation flow, reduce production cost,Improve production efficiency, the nickel-cobalt lithium manganate cathode material prepared by this method, the significant increase chemical property of material,It can prepare for industrialized production.
The present invention improves its technical problem using technical solution below to realize.
A kind of preparation method of nickel-cobalt lithium manganate cathode material provided by the invention, includes the following steps：
Liquid phase mixes：Three kinds of raw materials of nickel cobalt manganese are mixed in deionized water with lithium source, are stirred, prepares and presets solid contentMixed slurry.
Ball milling：The mixed slurry is subjected to wet ball grinding.
It is dry：Mixed slurry after ball milling is spray-dried, spherical shape mixed material is made.
Sintering：The spherical mixed material after the drying steps is positioned in atmosphere Muffle furnace, in air or500 DEG C are warming up to constant 10 DEG C/min to 15 DEG C/min in the atmosphere of oxygen, keeps the temperature 5h to 7h；Again with 20 DEG C/min to 25DEG C/min is warming up to 900 DEG C, 12h to 14h is kept the temperature, Temperature fall cooling obtains nickel-cobalt lithium manganate material.
It crushes：The nickel-cobalt lithium manganate material is crushed, and powder particle diameter control is in 1 μm to 20 μ ms.
Further, further include screening step after the pulverising step, the powder particle diameter is passed through to the sieve of 500 meshSieving inspection.
Further, in the liquid phase mixing step, three kinds of raw materials of the nickel cobalt manganese include nickel hydroxide, cobalt hydroxide,Manganese carbonate, the lithium source include lithium carbonate, and the nickel hydroxide, the cobalt hydroxide, the manganese carbonate, the lithium carbonate are matchedSet the mixed slurry that concentrations by weight is 40% to 50%.
Further, in the liquid phase mixing step, the nickel hydroxide, the cobalt hydroxide, the manganese carbonate be, instituteThe molar ratio for stating lithium carbonate is 6：2：2：5.25.
Further, in the liquid phase mixing step, three kinds of raw materials of the nickel cobalt manganese include nickel hydroxide, cobalt hydroxide,Manganese carbonate, the lithium source include lithium hydroxide, by the nickel hydroxide, the cobalt hydroxide, the manganese carbonate, the hydroxideLithium configures the mixed slurry that concentrations by weight is 40% to 50%.
Further, the nickel hydroxide, the cobalt hydroxide, the manganese carbonate, described in the liquid phase mixing stepThe molar ratio of lithium hydroxide is 6：2：2：5.25.
Further, in the mixed slurry, the molar ratio of lithium and nickel cobalt manganese system is 1.05：1 to 1.1：1；It is described mixedIt closes 25 minutes to 40 minutes a length of when the stirring of slurry.Preferably, the molar ratio of lithium and nickel cobalt manganese system is 1.05：1；It is described mixedIt closes 30 minutes a length of when the stirring of slurry.
Further, in the ball milling step, 6 hours are carried out extremely to the mixed slurry using ball mill or grinding aid machine8 hours ball millings, ball milling speed go to 3300 turns per minute for per minute 2800, ensure that material mixing is uniform and grain size reducesTo Nano grade.Ball-milling Time is preferably 6 hours, and ball milling speed is preferably 3000 turns per minute.
Further, in the drying steps, it is 250 DEG C to 310 DEG C to keep the inlet temperature of spraying device, outlet temperatureIt is 100 DEG C to 120 DEG C, gas flow 5.5m3/ h to 8m3/h.Preferably, inlet temperature is 300 DEG C, outlet temperature 110DEG C, gas flow 5.6m3/h。
Further, in the sintering step, the compressed gas being passed through in the Muffle furnace is 0.05MPa to 0.2MPa,Preferably 0.1MPa.
A kind of preparation method of nickel-cobalt lithium manganate cathode material provided by the invention has the beneficial effect of the following aspectsFruit：
The preparation method of nickel-cobalt lithium manganate cathode material provided by the invention, in deionized water by three kinds of materials of nickel cobalt manganeseAfter being thoroughly mixed with lithium source, then wet ball grinding is carried out, which compensates for the deficiency of solid phase mixing, fromAnd the material after wet ball grinding is realized and mixes uniform and grain size nanosizing, keeps nickel cobalt manganese respectively abundantIt plays a role, improves the performance of nickel-cobalt lithium manganate cathode material.And make the shape of nickel-cobalt lithium manganate cathode material closerCircle greatly improves the chemical property of nickel-cobalt lithium manganate cathode material.The preparation side of the nickel-cobalt lithium manganate cathode materialMethod can effectively solve the problem that the uniform sex chromosome mosaicism of raw material mixing, can also simplify technical operation flow, reduce production cost, improve lifeEfficiency is produced, there is great application value and market competition advantage.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present inventionIn attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment isA part of the embodiment of the present invention, instead of all the embodiments.The present invention being usually described and illustrated herein in the accompanying drawings is implementedThe component of example can be arranged and be designed with a variety of different configurations.
Therefore, below the detailed description of the embodiment of the present invention to providing in the accompanying drawings be not intended to limit it is claimedThe scope of the present invention, but be merely representative of the present invention selected embodiment.Based on the embodiments of the present invention, this field is commonThe every other embodiment that technical staff is obtained without creative efforts belongs to the model that the present invention protectsIt encloses.
In the description of the present invention, it is to be understood that, the orientation or positional relationship of the instructions such as term "upper", "lower" is baseIn orientation or positional relationship shown in the drawings, or product of the present invention using when the orientation or positional relationship usually put, orPerson is the orientation or positional relationship that those skilled in the art usually understand, is merely for convenience of description of the present invention and simplification of the description,It does not indicate or imply the indicated equipment or element must have a particular orientation, with specific azimuth configuration and operation, becauseThis is not considered as limiting the invention.
" first ", " second " etc. of the present invention, is only used to distinguish between description, has no special meaning.
In the description of the present invention, it is also necessary to which explanation is unless specifically defined or limited otherwise, term " setting "," installation " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；Can beIt is connected directly, it can also be indirectly connected through an intermediary.It for the ordinary skill in the art, can be with concrete conditionUnderstand the concrete meaning of above-mentioned term in the present invention.
Fig. 1 is a kind of flow chart of the preparation method for nickel-cobalt lithium manganate cathode material that the specific embodiment of the invention provides,Please refer to Fig. 1.
A kind of preparation method of nickel-cobalt lithium manganate cathode material provided in this embodiment, including it is liquid phase mixing, ball milling, dryDry, sintering, crushing and the several steps of screening：
Nickel hydroxide, cobalt hydroxide, manganese carbonate and lithium hydroxide or lithium carbonate are sufficiently mixed in deionized waterStirring, after wet ball grinding 6h, the spherical mixed material of certain particle size range is made up of spray drying process.In air or oxygenIn the Muffle furnace that atmosphere is enclosed, under the conditions of compressed air is 0.1MPa, it is warming up to 500 DEG C of heat preservation 5h；It is warming up to 900 DEG C of heat preservations again12h obtains nickle cobalt lithium manganate spheric granules.Obtained mixture material is ground into 3 μm to 15 μm through high power pulverizerGrain, obtains nickel cobalt manganese lithium anode material after sieving.
Specific operating process is as follows：
S1, liquid phase mixing：Three kinds of raw materials of nickel cobalt manganese are mixed in deionized water with lithium source, are stirred, mixed slurry is made.Three kinds of raw materials of nickel cobalt manganese include nickel hydroxide, cobalt hydroxide, manganese carbonate, and lithium source includes lithium carbonate or lithium hydroxide, by aforementioned originalMaterial is stirred, is sufficiently mixed in deionized water according to a certain percentage, and mixed slurry is made.
Preferably, nickel hydroxide be 6mol, cobalt hydroxide 2mol, manganese carbonate 2mol, lithium carbonate be 5.25mol orPerson's lithium hydroxide is that 10.5mol is mixed, and the molar ratio of lithium and nickel cobalt manganese system is 1.05：1, mixed slurry obtained is matchedIt is 40% to 50% to set concentrations by weight.
S2, ball milling：The mixed slurry that above-mentioned configuration concentrations by weight is 40% to 50% is subjected to wet ball grinding, is made oneDetermine the mixed slurry of solid content.Ball mill or the equipment such as grinding aid machine or colloidal mill may be used in ball milling.Ball-milling Time controlsAt 6 hours or so, ball milling speed was about 3000 turns per minute.
S3 is dry：Mixed slurry after ball milling is spray-dried, the spherical mixture of certain particle size range is madeMaterial.When spray drying, the inlet temperature for controlling spraying device is 300 DEG C, and outlet temperature is 110 DEG C, gas flow 5.6m3/h。
S4, sintering：Spherical mixed material after spray drying is positioned in the atmosphere Muffle furnace of high temperature, in air or500 DEG C are warming up to constant 10 DEG C/min in the atmosphere of oxygen, keeps the temperature 5h；900 DEG C are warming up to 20 DEG C/min again, keeps the temperature 12h,Temperature fall cools down, and obtains nickel-cobalt lithium manganate material.
S5 is crushed：Nickel-cobalt lithium manganate material is crushed, and powder particle diameter control is in 1 μm to 20 μ ms.
S6, screening：By powder particle diameter by the sieve sieving inspection of 500 mesh.Certainly, it is not limited in selecting 500 purposesSieve selects suitable sieve to be sorted according to actual conditions.
First embodiment
Manganese carbonate 230g is weighed, 2048.3g deionizations are added as in beaker in cobalt hydroxide 186g, nickel hydroxide 558gWater stirs 10min, adds lithium carbonate 391.5g (purity 99.26%), stirs 20min, at this time the solid content of mixed slurryIt is 40%.Ball mill ball milling mixing slurry is opened, with the rate ball milling 6h of 3000rpm/min, solid content is obtained and is 39.6%, gluesDegree is the mixture of 7324.1MPa.
Mixture after ball milling is subjected to spray drying granulating, spray dryer parameter is set as：300 DEG C of inlet temperature,Outlet temperature is 110 DEG C, and throughput is set as 5.6m3/ h, the spherical mixed material after being spray-dried.Take the above-mentioned balls of 350gShape mixed material is sintered in atmosphere Muffle furnace, compressed air 0.1MPa, and temperature is to be warming up to 500 DEG C with 10 DEG C/min5h is kept the temperature, then 900 DEG C of heat preservation 12h, natural cooling cooling are warming up to 20 DEG C/min.Material through oversintering is subjected to 500 meshSieve sieving, obtain LiNi0.6Co0.2Mn0.2O2Powdery electrode material.
The powder tap density of synthesis is 2.32g/m3, specific surface area 0.50m2/g.It is anode, lithium with the material of gainedPiece is that cathode is assembled into button cell, and conductive agent uses super " p ", diaphragm celgard2300, electrolyte to select 1mol/LLiPF6Conductive salt and DMC：DEC：EC (wt%)=1：1：1 solvent.The discharge capacity measured under 0.2C discharging conditions is180.5mAh/g, the special capacity fade 0.4% after 30 cycles.The cycle-index of first embodiment and the pass of specific discharge capacitySystem, as shown in Figure 2.
Second embodiment
Manganese carbonate 230g is weighed, 2048.3g deionizations are added as in beaker in cobalt hydroxide 186g, nickel hydroxide 558gWater stirs 10min, adds lithium hydroxide 441.0g (single crystals water), stirs 20min, and the solid content of mixed slurry is at this time40%.Ball mill ball milling mixing slurry is opened, with the rate ball milling 6h of 3000rpm/min, it is 39.8%, viscosity to obtain solid contentFor the mixed slurry of 8324.1MPa.
Mixture after ball milling is subjected to spray drying granulating, spray dryer parameter is set as：300 DEG C of inlet temperature,Outlet temperature is 110 DEG C, and throughput is set as 5.6m3/ h, the spherical mixed material after being spray-dried.Take the above-mentioned balls of 350gShape mixed material is sintered in atmosphere Muffle furnace, compressed air 0.1MPa, and temperature is to be warming up to 500 DEG C with 10 DEG C/min7h is kept the temperature, then 900 DEG C of heat preservation 12h, natural cooling cooling are warming up to 20 DEG C/min.Material through oversintering is subjected to 500 meshSieve sieving, obtain LiNi0.6Co0.2Mn0.2O2Powdery electrode material.
The powder tap density of synthesis is 2.42g/m3, specific surface area 0.49m2/g.It is anode, lithium with the material of gainedPiece is that cathode is assembled into button cell, and conductive agent uses super " p ", diaphragm celgard2300, electrolyte to select 1mol/LLiPF6Conductive salt and DMC：DEC：EC (wt%)=1：1：1 solvent.The discharge capacity measured under 0.2C discharging conditions is179.5mAh/g, the special capacity fade 0.6% after 30 cycles.The cycle-index of second embodiment and the pass of specific discharge capacitySystem, as shown in Figure 3.
3rd embodiment
Manganese carbonate 230g is weighed, 1668.9g deionizations are added as in beaker in cobalt hydroxide 186g, nickel hydroxide 558gWater stirs 10min, adds lithium carbonate 391.5g (purity 99.26%), stirs 20min, at this time the solid content of mixed slurryIt is 45%.Ball mill ball milling mixing slurry is opened, with the rate ball milling 6h of 3000r/min, it is 43.8%, viscosity to obtain solid contentFor the mixture of 8693.6MPa.
Mixture after ball milling is subjected to spray drying granulating, spray dryer parameter is set as：280 DEG C of inlet temperature,Outlet temperature is 110 DEG C, and throughput is set as 5.6m3/ h, the spherical mixed material after being spray-dried.Take the above-mentioned balls of 350gShape mixed material is sintered in atmosphere Muffle furnace, compressed air 0.1MPa, and temperature is to be warming up to 520 DEG C with 10 DEG C/min5h is kept the temperature, then 920 DEG C of heat preservation 12h, natural cooling cooling are warming up to 20 DEG C/min.Material through oversintering is subjected to 500 meshSieve sieving, obtain LiNi0.6Co0.2Mn0.2O2Powdery electrode material.
The powder tap density of synthesis is 2.34g/m3, specific surface area 0.56m2/g.It is anode, lithium with the material of gainedPiece is that cathode is assembled into button cell, and conductive agent uses super " p ", diaphragm celgard2300, electrolyte to select 1mol/LLiPF6Conductive salt and DMC：DEC：EC (wt%)=1：1：1 solvent.The discharge capacity measured under 0.2C discharging conditions is176.5mAh/g, the special capacity fade 0.7% after 30 cycles.The cycle-index of 3rd embodiment and the pass of specific discharge capacitySystem, as shown in Figure 4.
The nickle cobalt lithium manganate anode material that specific embodiment provides through the invention it can be seen from above-mentioned three groups of test datasThe preparation method of material, for positive electrode obtained after carrying out multiple discharge experiment, special capacity fade is all relatively low, is embodying this justThe excellent chemical property of pole material.
A kind of preparation method of nickel-cobalt lithium manganate cathode material provided by the invention has the beneficial effect of the following aspectsFruit：
The preparation method of nickel-cobalt lithium manganate cathode material provided by the invention, in deionized water by three kinds of raw materials of nickel cobalt manganeseAfter being thoroughly mixed with lithium source, ball mill is recycled to carry out wet ball grinding, it is mixed which compensates for solid phaseThe deficiency of conjunction makes nickel cobalt so that the material after wet ball grinding, which can be realized, mixes uniform and grain size nanosizingManganese respectively plays one's part to the full, and improves the performance of nickel-cobalt lithium manganate cathode material.And after carrying out ball milling so that nickle cobalt lithium manganateThe shape of positive electrode greatly improves the chemical property of nickel-cobalt lithium manganate cathode material closer to circle.The nickel cobalt manganeseThe preparation method of sour lithium anode material can effectively solve the problem that the uniform sex chromosome mosaicism of raw material mixing, can also simplify technological operation streamJourney reduces production cost, improves production efficiency, has great application value and market competition advantage.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this fieldFor art personnel, the present invention can have various changes, combination and variation.All within the spirits and principles of the present invention, made byAny modification, equivalent substitution, improvement and etc. should all be included in the protection scope of the present invention.