CN100452488C - Preparation method of ternary compound potassium ion battery plus plate material - Google Patents
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Abstract
A method for preparing positive electrode material of ternary composite Li ion cell includes mixing soluble compound of Ni and Mn as well as Co to be transition metal soluble, filling certain amount of ammonia water in reactor then adding transition metal solution into reactor by ejecting gun and pumping mixed liquid of ammonia and sodium hydroxide into reactor by precipitation then wet-mixing it with Li compound, sintering mixture of presoma and Li compound with high temperature under oxygen atmosphere then grinding sintered material to obtain positive electrode material.
Description
Technical field
The present invention relates to lithium ion battery, particularly relate to a kind of transition metal and be easy to oxidation, the high temperature sintering time is short, the preparation method of the ternary compound potassium ion battery plus plate material that preparation cost is low.
Background technology
Lithium ion battery is because of having characteristics such as energy height, long service life, low pollution, and is used widely in various fields such as portable portable electronic equipment, electric automobiles.In occupation of most important status, the quality of its performance has directly determined the performance of final secondary cell product to positive electrode in lithium ion battery structure, and its performance and price can directly have influence on the performance and the price of lithium-ions battery.
Along with popularizing rapidly of portable electric appts, more and more higher to the requirement of battery performance, simultaneously must be also more and more higher to the performance requirement of material.Therefore, the positive electrode of high voltage, high-energy-density becomes the focus of research.LiCoO
2(cobalt acid lithium) becomes the preferred material of present commercial li-ion anode because of advantages such as its manufacture craft is simple, material thermal stability and good cycle.But the effective rate of utilization of lithium is about 60% in the cobalt acid lithium, and LiCoO
2The embedding amount of taking off and its charging voltage positive correlation of middle lithium, when increasing to 4.5V as charging voltage by 4.2V, the specific capacity of electrode increases to 170～180mAh/g from 140～150mAh/g.Yet discover, the electrode cyclical stability variation after overcharging, capacity attenuation is exceedingly fast, and the fail safe of battery simultaneously is variation also.LiNiO
2(lithium nickelate) charging and discharging capacity height, but poor heat stability.LiMn
2O
4(LiMn2O4) Heat stability is good, but capacity is on the low side again.Therefore Li-Ni-Mn-Co-O (the LiNi that integrates three's advantage
xMn
yCo
1-x-yO
2) become the focus of research.
About LiNi
xMn
yCo
1-x-yO
2The preparation and the bibliographical information of aspect of performance more, its preparation method comprises high temperature solid-state method, sol-gal process etc.Chinese patent CN200410019741 discloses a kind of preparation method of Postive electrode material of li-ion accumulator, and it is to prepare manganous hydroxide nickel cobalt precursor with coprecipitation method, mixes the back again with the lithium source and makes positive electrode by high temperature solid state reaction.Another Chinese patent CN1614801 discloses a kind of lithium ion battery multi-element composite positive pole material and preparation method thereof, it is raw material that this method is selected nickel, cobalt, manganese compound for use, mix with aqueous slkali after being mixed with solution, add certain quantity of additive simultaneously, by the precipitation of continuous stirring generation homogeneous, at high temperature obtain multi-element composite positive pole material after calcining, the refinement after the mixing and ball milling in proportion with lithium compound then.When coprecipitation prepared manganous hydroxide nickel cobalt precursor, most methods that drip that adopt caused producing local overrich phenomenon in the zonule that drop drips, and form a large amount of nucleus, make the precipitation pattern be difficult to control.U.S. Pat 2004191161 discloses a kind of lithium nickel cobalt metal oxide and preparation method thereof, and this method is a raw material with lithium compound, nickel hydroxide cobalt, metallic compound, prepares lithium nickel cobalt manganese oxygen by high temperature solid-state method.But the simple mixing by transistion metal compound is difficult to make three kinds of transition metal evenly to distribute, and does not reach the Expected Results of doping.
Summary of the invention
The present invention is intended to address the above problem, and provides a kind of transition metal to be easy to oxidation, and the high temperature sintering time is short, the preparation method of the ternary compound potassium ion battery plus plate material that preparation cost is low.
For achieving the above object, the invention provides a kind of preparation method of ternary compound potassium ion battery plus plate material, this method comprises the steps:
A, soluble nickel, manganese, cobalt compound are mixed into transition metal solution by the molal quantity of x: y: 1-x-y, wherein, 0.1≤x≤0.6,0≤y≤0.6,0.1≤x+y≤0.9;
In this step, described nickel compound can be nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate; Manganese compound can be manganese nitrate, manganese sulfate, manganese chloride or manganese acetate; Cobalt compound can be cobalt nitrate, cobaltous sulfate, cobalt chloride or cobalt acetate.
B, be that 5～20% ammoniacal liquor adds in the reactor and reaches 3～10cm height, feed compressed air from reactor bottom and stir concentration.The gas that this step adopted stirs has increased oxygen and contacting that transition metal hydroxide precipitates, and is beneficial to the oxidation that is deposited under the alkali condition.Adopt gas to stir simultaneously,, sediment is produced buoyancy, prolonged the sedimentation time, help forming the satisfied presoma of producing the presoma granularity requirements because gas enters from reactor bottom.
C, in reactor, spray into described transition metal solution with spray gun, in reactor, pump into the mixed liquor of ammonia and NaOH simultaneously by servopump, the mixed liquor of described ammonia and NaOH atomizes under compressed-air actuated effect, fully mix with the transition metal solution that spray gun sprays into, generate the presoma precipitation of homogeneous; Described atomizing comprises the relative position of the inlet that enters reactor by the outlet of ammonia that reactor is set and NaOH mixed liquor and Compressed Gas and/or regulates compressed-air actuated pressure and realize.Finish when transition metal mixed solution sprays, reaction system reaches the pH value of setting, and keeps stable, stops pump ammonia and NaOH mixed liquor in reactor.Presoma is oxidized in coprecipitation process.
In this step, described transition metal solution sprays into from reactor head with spray gun, and the Compressed Gas that stirs usefulness then is to feed from reactor bottom, and the jet velocity that adds the transition metal solution of reactor is 0.2～2 liter/hour.The outlet of the ammonia of reactor and NaOH mixed liquor is located at the inlet that Compressed Gas enters reactor, and mixed liquor is atomizing rapidly under the compressed air effect.The amount of pumping into of the mixed liquor of described ammonia and NaOH and the speed that pumps into are controlled by the pH value of reaction system, and this pH value is controlled in 9.5～12.5 scopes.The pH value is measured by pH meter, and pH meter outputs a control signal to servopump, and the addition of control ammonia and NaOH mixed liquor remains in the pH value scope of setting reaction system.
The ammonia in this step and the mixed liquor of NaOH are as precipitation reagent, and ammoniacal liquor plays precipitation reagent and complexing agent effect simultaneously, and it had both made precipitation reagent, the NH that decomposites simultaneously when presoma prepares
4 +Form complex ion, controls reaction speed with the transition metal ions complexing again; Add transition metal solution with injection method and can avoid local overrich phenomenon.
D, with the presoma sedimentation and filtration, dry, sieve back and lithium compound be that 1: 1～1.3: 1 ratio is carried out wet mixing and closed in the ratio of the total atomicity of the molal quantity of lithium atom and nickel manganese cobalt, mixes slowly evaporating solvent of back;
Lithium compound in this step is organic salt, lithium hydroxide, lithia or the lithium peroxide of lithium.
E, the mixture of presoma and lithium compound is carried out high temperature sintering under oxygen atmosphere, sintered product through grind, screening, making molecular formula is LiNi
xMn
yCo
1-x-yO
2Positive electrode.
Described high temperature sintering is that the heating rate with 1～20 ℃/min is warmed up to 650～750 ℃, insulation 4～10h, and the heating rate with 1～10 ℃/min is warmed up to 850～1000 ℃ then, and insulation 8～24h cools off with stove.
With existing LiNi
xMn
yCo
1-x-yO
2The preparation method compares, and the present invention has following distinguishing feature:
One, owing to adopt spray-on process to add transition metal solution, avoided local overrich phenomenon.
Two, in preparation process of precursor, adopt gas to stir, increased oxygen and contacting that transition metal hydroxide precipitates, be beneficial to the oxidation that is deposited under the alkali condition.Because when gas stirred, gas entered from reactor bottom, sediment is produced buoyancy, prolonged the sedimentation time, help forming the presoma that satisfies granularity requirements.
Three, presoma is oxidized in coprecipitation process, has shortened the high temperature sintering time, has reduced preparation cost.
Four, the ternary composite positive pole LiNi of method preparation of the present invention
xMn
xCo
1-2xO
2Discharge and recharge at the 3.0-4.4V potential region, all more than 170mAh/g, 100 circulation volume conservation rates of 1C multiplying power discharging are all more than 92% for first discharge specific capacity.
Five, the ternary composite positive pole of method preparation of the present invention mixes because of Ni, Mn, three kinds of transition metal of Co, and the three acts synergistically, and has stablized the layer structure of material, has improved charge/discharge capacity, cycle performance and the overcharging resisting performance of material.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Embodiment 1
It is 3 moles nickel nitrate, manganese nitrate, cobalt nitrate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 1: 1: 1 ratio, be made into the solution that concentration is 3mol/L, the NaOH that takes by weighing total amount simultaneously and be 5 moles is made into the solution that concentration is 2mol/L, treat that solution cooling back adds certain amount of ammonia water (amount of ammoniacal liquor can be determined according to the ratio of back), the mol ratio of ammonia and NaOH is 3: 10.
In reactor, add the dark ammonia spirit of 5cm, open the compressed air valve, by gas flowmeter control stirring intensity.When the ammonia spirit in the reactor stirs, add the transition metal mixed solution with spray gun in reactor, open the servopump by pH meter control simultaneously, servopump pumps into the mixed liquor of ammoniacal liquor and NaOH in pH meter control downhill reaction device, the pH value is controlled at 10, forms Ni
1/3Mn
1/3Co
1/3(OH)
2Presoma.
Take by weighing the LiOHH of 100 grams
2O (a hydronium(ion) oxidation lithium), being dissolved in quality is LiOHH
2The deionized water that O is four times, in the presoma after the ratio adding oven dry of lithium/(nickel+manganese+cobalt)=1.05, slow evaporating solvent makes the lithium hydroxide secondary crystallization under stirring condition.This mixture is carried out high temperature sintering, be warmed up to 650 ℃ with the heating rate of 10 ℃/min, insulation 10h, the heating rate with 5 ℃/min is warmed up to 850 ℃ again, and insulation 20h cools off with stove then.Cooled material is crossed 300 mesh sieves through ball mill crushing, promptly gets end product LiNi
1/3Mn
1/3Co
1/3O
2
LiNi
1/3Mn
1/3Co
1/3O
2First discharge specific capacity 170.3mAh/g, after the 1C rate charge-discharge 100 times circulation, capability retention is 94.7%.
Embodiment 2
Nickel, manganese, cobalt are taken by weighing nickel nitrate, manganese nitrate, cobalt nitrate in 2: 2: 1 ratio, be made into the solution that concentration is 3mol/L, all the other conditions are with example 1, and end product is LiNi
0.4Mn
0.4Co
0.2O
2First discharge specific capacity is all at 171.2mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 93.2%.
Embodiment 3
It is 6 moles nickel nitrate, manganese nitrate, cobalt nitrate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 1: 1: 1 ratio, be made into the solution that concentration is 4mol/L, the NaOH that takes by weighing total amount simultaneously and be 9 moles is made into the solution that concentration is 3mol/L, treat that solution cooling back adds the ammoniacal liquor of a certain amount of (can determine according to the ratio of back), the mol ratio of ammonia and NaOH is 1: 2.All the other conditions form Ni with embodiment 1
1/3Mn
1/3Co
1/3(OH)
2Presoma; Take by weighing the LiOHH of 200 grams
2O (a hydronium(ion) oxidation lithium), being dissolved in quality is LiOHH
2The deionized water that O is three times is in the presoma after the ratio adding oven dry of lithium/(nickel+manganese+cobalt)=1.05, slow evaporating solvent under stirring condition.This mixture is carried out high temperature sintering, and sintering atmosphere is an oxygen, is warmed up to 700 ℃ with the heating rate of 10 ℃/min, insulation 6h, and the heating rate with 5 ℃/min is warmed up to 900 ℃ again, and insulation 12h cools off with stove.Cooled material is crossed 300 mesh sieves through ball mill crushing, promptly gets end product LiNi
1/3Mn
1/3Co
1/3O
2First discharge specific capacity is all at 170.8mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 94.8%.
Embodiment 4
It is 3 moles nickelous sulfate, manganese sulfate, cobaltous sulfate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 1: 1: 1 ratio, be made into the solution that concentration is 2mol/L, the NaOH that takes by weighing total amount simultaneously and be 4 moles is made into the solution that concentration is 3mol/L, treat that solution cooling back adds the ammoniacal liquor of a certain amount of (ratio according to the back is determined), the mol ratio of ammonia and NaOH is 3: 5.In reactor, add the dark ammonia spirit of 5cm, open the compressed air valve, by gas flowmeter control stirring intensity.When the ammonia spirit in the reactor stirs, add the transition metal mixed solution with spray gun in reactor, open the servopump by pH meter control simultaneously, servopump pumps into ammoniacal liquor and NaOH mixed liquor in pH meter control downhill reaction device, the pH value is controlled at 10.5, forms Ni
1/3Mn
1/3Co
1/3(OH)
2Presoma; The LiOHH of weighing 100 grams
2O, being dissolved in quality is LiOHH
2The deionized water that O is four times is in the presoma after the ratio adding oven dry of lithium/(nickel+manganese+cobalt)=1.04, slow evaporating solvent under stirring condition.The high temperature sintering condition gets end product LiNi with embodiment 3
1/3Mn
1/3Co
1/3O
2First discharge specific capacity is all at 170.6mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 94.6%.
Embodiment 5
It is 5 moles nickelous sulfate, manganese nitrate, cobaltous sulfate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 2: 2: 1 ratio, be made into the solution that concentration is 3mol/L, the NaOH that takes by weighing total amount simultaneously and be 5.5 moles is made into the solution that concentration is 3mol/L, treat that solution cooling back adds the ammoniacal liquor of a certain amount of (ratio according to the back is determined), the mol ratio of ammonia and NaOH is 1: 1; All the other conditions get end product LiNi with embodiment 4
0.4Mn
0.4Co
0.2O
2First discharge specific capacity is all at 172.7mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 93.4%.
Embodiment 6
It is 4 moles nickel nitrate, manganese nitrate, cobalt nitrate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 3: 3: 2 ratio, be made into the solution that concentration is 2mol/L, the NaOH that takes by weighing total amount simultaneously and be 5 moles is made into the solution that concentration is 2mol/L, treat that solution cooling back adds the ammoniacal liquor of a certain amount of (ratio according to the back is determined), the mol ratio of ammonia and NaOH is 4: 5.In reactor, add the dark ammonia spirit of 5cm, open the compressed air valve, by gas flowmeter control stirring intensity.When the ammonia spirit in the reactor stirs, add the transition metal mixed solution with spray gun in reactor, open the servopump by pH meter control simultaneously, servopump pumps into the mixed liquor of ammoniacal liquor and NaOH in pH meter control downhill reaction device, the pH value is controlled at 10.5, forms Ni
0.375Mn
0.375Co
0.25(OH)
2Presoma.Take by weighing the CH of 300 grams
3COOLi2H
2O (Chinese two hydration lithium acetates), being dissolved in quality is CH
3COOLi2H
2The deionized water that O is three times is in the presoma after the ratio adding oven dry of lithium/(nickel+manganese+cobalt)=1.06, slow evaporating solvent under stirring condition.This mixture is carried out high temperature sintering, be warmed up to 750 ℃ with the heating rate of 10 ℃/min, insulation 10h, the heating rate with 5 ℃/min is warmed up to 1000 ℃ again, and insulation 12h cools off with stove.Cooled material is crossed 300 mesh sieves through ball mill crushing, promptly gets end product LiNi
0.375Mn
0.375Co
0.25O
2First discharge specific capacity is all at 173.2mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 92.1%.
Comparative Examples 1
It is 3 moles nickel nitrate, manganese nitrate, cobalt nitrate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 1: 1: 1 ratio, be made into the solution that concentration is 3mol/L, the NaOH that takes by weighing total amount simultaneously and be 5 moles is made into the solution that concentration is 2mol/L, treat that solution cooling back adds certain amount of ammonia water, the mol ratio of ammonia and NaOH is 3: 10.Add the dark ammonia spirit of 5cm in reactor, adopt the dropping mode to add the transition metal mixed solution in reactor, the pH value is controlled at 10, servopump pumps into ammoniacal liquor and NaOH mixed liquor in pH meter control downhill reaction device, mixed liquor adopts gas to stir also without atomizing, forms Ni
1/3Mn
1/3Co
1/3(OH)
2Presoma.High-sintering process is with embodiment 1, and cooled material is crossed 300 mesh sieves through ball mill crushing, promptly gets end product LiNi
1/3Mn
1/3Co
1/3O
2First discharge specific capacity is all at 166.8mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 87.2%.
Comparative Examples 2
It is 3 moles nickel nitrate, manganese nitrate, cobalt nitrate that nickel, manganese, cobalt are taken by weighing three kinds of total amounts of atom in 1: 1: 1 ratio, be made into the solution that concentration is 4mol/L, taking by weighing total amount simultaneously is that several 4.5 moles NaOH is made into the solution that concentration is 3mol/L, treat that solution cooling back adds the ammoniacal liquor of a certain amount of (ratio according to the back is determined), the mol ratio of ammonia and NaOH is 1: 2.Adopt mixer to stir, adopt spray-on process to add transition metal solution, pH value is controlled at 10, the mixed liquor of servopump dropping ammonia and NaOH in pH meter control downhill reaction device, formation Ni
1/3Mn
1/3Co
1/3(OH)
2Presoma.Batching, high-sintering process is with embodiment 3, end product LiNi
1/3Mn
1/3Co
1/3O
2First discharge specific capacity is all at 167.4mAh/g, and after 100 circulations of 1C rate charge-discharge, capability retention is 88.7%.
Claims (9)
1, a kind of preparation method of ternary compound potassium ion battery plus plate material is characterized in that, it comprises the steps:
A, soluble nickel, manganese, cobalt compound are mixed into transition metal solution by the molal quantity of x: y: 1-x-y, wherein, 0.1≤x≤0.6,0≤y≤0.6,0.1≤x+y≤0.9;
B, be that 5～20% ammoniacal liquor adds in the reactor and reaches 3～10cm height, feed compressed air from reactor bottom and stir concentration;
C, in reactor, spray into described transition metal solution with spray gun, in reactor, pump into the mixed liquor of ammonia and NaOH simultaneously by servopump, the mixed liquor of described ammonia and NaOH atomizes under compressed-air actuated effect, fully mix with the transition metal solution that spray gun sprays into, generate the presoma precipitation of homogeneous; Described atomizing comprises the relative position of the inlet that enters reactor by the outlet of ammonia that reactor is set and NaOH mixed liquor and Compressed Gas and/or regulates compressed-air actuated pressure and realize;
D, with the presoma sedimentation and filtration, dry, sieve back and lithium compound be that 1: 1～1.3: 1 ratio is carried out wet mixing and closed in the ratio of the total atomicity of the molal quantity of lithium atom and nickel manganese cobalt, mixes slowly evaporating solvent of back;
E, the mixture of presoma and lithium compound is carried out high temperature sintering under oxygen atmosphere, sintered product through grind, screening, making molecular formula is LiNi
xMn
yCo
1-x-yO
2Positive electrode.
2, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 1 is characterized in that, among the step a, described nickel compound can be nickel nitrate, nickelous sulfate, nickel chloride or nickel acetate; Manganese compound can be manganese nitrate, manganese sulfate, manganese chloride or manganese acetate; Cobalt compound can be cobalt nitrate, cobaltous sulfate, cobalt chloride or cobalt acetate.
3, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 1 is characterized in that, among the step c, the jet velocity that adds the transition metal solution of reactor is 0.2～2 liter/hour.
4, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 3 is characterized in that, described transition metal solution sprays into from reactor head with spray gun, and the Compressed Gas that stirs usefulness then is to feed from reactor bottom.
5, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 1, it is characterized in that, among the step c, the outlet of the ammonia of reactor and NaOH mixed liquor is located at the inlet that Compressed Gas enters reactor, and mixed liquor is atomizing rapidly under the compressed air effect.
6, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 5, it is characterized in that, among the step c, the amount of pumping into of the mixed liquor of described ammonia and NaOH and the speed that pumps into are controlled by the pH value of reaction system, and this pH value is controlled in 9.5～12.5 scopes.
7, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 6, it is characterized in that, the pH value of mixed liquor is measured by pH meter in the reactor, pH meter outputs a control signal to servopump, the addition of control ammonia and NaOH mixed liquor remains in the pH value scope of setting reaction system.
8, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 1 is characterized in that, in the steps d, described lithium compound is organic salt, lithium hydroxide, lithia or the lithium peroxide of lithium.
9, the preparation method of ternary compound potassium ion battery plus plate material as claimed in claim 1, it is characterized in that, among the step e, described high temperature sintering is that the heating rate with 1～20 ℃/min is warmed up to 650～750 ℃, insulation 4～10h, heating rate with 1～10 ℃/min is warmed up to 850～1000 ℃ then, and insulation 8～24h cools off with stove.
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| CN101630736B (en) * | 2009-08-17 | 2011-11-02 | 深圳市天骄科技开发有限公司 | Improvement method of cycle performance of lithium battery tertiary cathode material |
| CN106395918A (en) * | 2009-10-22 | 2017-02-15 | 户田工业株式会社 | Nickel-cobalt-manganese compound particle powder and method for producing same, lithium composite oxide particle powder and method for producing same, and nonaqueous electrolyte secondary battery |
| MX340839B (en) * | 2010-12-30 | 2016-07-27 | Yava Tech Inc | Transition metal compound particles and methods of production. |
| CN102513541A (en) * | 2012-01-17 | 2012-06-27 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-cobalt-manganese alloy powder |
| CN103178252B (en) * | 2013-03-18 | 2016-01-20 | 昆明理工大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN103606666A (en) * | 2013-11-19 | 2014-02-26 | 江苏天鹏电源有限公司 | Stable lithium ion battery with high capacitance |
| CN103746111B (en) * | 2014-01-28 | 2015-10-28 | 天津先众科技有限公司 | A kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof |
| DE102014219421A1 (en) * | 2014-09-25 | 2016-03-31 | Bayerische Motoren Werke Aktiengesellschaft | Cathode (positive electrode) and this comprehensive lithium ion battery in the state before the first charging, method for forming a lithium-ion battery and lithium ion battery after formation |
| CN104393278B (en) * | 2014-10-29 | 2017-01-18 | 新乡天力锂能股份有限公司 | Preparation method of nickel cobalt lithium manganate ternary material |
| CN107464929B (en) * | 2017-08-01 | 2020-08-28 | 北方奥钛纳米技术有限公司 | Preparation method of nickel cobalt lithium manganate cathode material, lithium ion battery cathode material and lithium ion battery |
| CN109755600B (en) * | 2019-01-29 | 2022-08-05 | 天津大学 | Carbon cloth loaded nickel-cobalt-oxygen nanosheet composite material, preparation method thereof and application of electrode |
| CN112371067B (en) * | 2020-06-10 | 2022-09-02 | 成都思达能环保设备有限公司 | Preparation method and system of positive electrode material precursor |
| CN113178565B (en) * | 2021-03-29 | 2023-06-16 | 广东邦普循环科技有限公司 | Mixing process for preparing high-nickel anode material and application thereof |
| CN117923561A (en) * | 2023-08-11 | 2024-04-26 | 天津国安盟固利新材料科技股份有限公司 | Monocrystal or monocrystal-like lithium-rich manganese-based positive electrode material precursor, and preparation method and application thereof |
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