CN107732232A - A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material - Google Patents
A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material, during lithium source is mixed into, nickel cobalt manganese presoma and lithium source hydro-thermal method are reacted into 20 ~ 30h synthesis at 160 ~ 250 DEG C；Resulting material is dried, being placed in 700 ~ 980 DEG C of 6 ~ 16h of heat preservation sintering in Muffle furnace after broken obtains nickel-cobalt lithium manganate cathode material.The present invention has following beneficial effect：By hydrothermal synthesis method, presoma and the low temperature crystallization of lithium source are realized, avoids the waste in being stirred to lithium source and local mixing non-uniform phenomenon；Material internal crystal defect prepared by Hydrothermal Synthesiss is small, reduces in sintering process because the control of temperature is to the influence factor of material crystalline degree, reduces calcining heat and the time of material, saved cost；The preparation method of the present invention causes positive electrode to have higher discharge capacity and more excellent cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, a kind of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material of specific design
Preparation method.
Background technology
Lithium ion battery because with energy density it is high, have extended cycle life, be in light weight, self discharge is small and the spy such as environment-friendly
Point is widely used to the fields such as small-sized electronic product, energy automobile.At present, the positive pole of lithium ion battery is mainly nickel cobalt mangaic acid
Lithium anode material, its production technology are that coprecipitation produces presoma, are burnt with the lithium source mixed at high speed such as lithium carbonate, then high temperature solid-state
Knot, crush to obtain.
Mixed lithium sintering is carried out in high-temperature sintering process again after being mixed using high-speed stirred, due to the Overdosing problems and ring of lithium source
Border, the influence of moisture, the alkali compounds that positive electrode surface can be excessive remnants, surface alkalinty compound add irreversible appearance
Amount loss, while deteriorate lithium battery cycle performance, the security performance of lithium ion battery is hidden some dangers for；Mixed lithium sintering is using at a high speed
Carrying out high temperature sintering after being stirred again, the difference of temperature is the main reason for causing its crystal inside defect in sintering process,
So as to influence the quality of battery.
The preparation method of a kind of polynary positive pole material as described in number of patent application CN201310107255.3, by forerunner
Suspension slurry is formed with metallic compound again after body, lithium source mixed calcining, calcining again obtains intermediate product；Repeatedly sintering and
Crystal defect is produced, reduces the service life of lithium battery.One kind described in another number of patent application CN201310020961.4
Alumina-coated be modified lithium nickel cobalt manganese oxygen positive electrode preparation method, by presoma, Doped ions salting liquid be dispersed in from
In sub- water, product is obtained with lithium salts mixed sintering after being calcined, it is uneven not there is the waste of lithium source and local mixing
Foot.
In summary, existing nickel-cobalt lithium manganate cathode material there is because repeatedly sintering and caused by crystal defect, and
It is stirred the alkali compounds of the waste for causing lithium source and the uneven deficiency, the in addition surface of positive electrode of local mixing
Remnants it is excessive, further have impact on the service life of lithium battery.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material, it passes through water
Process for thermosynthesizing, presoma and the low temperature crystallization of lithium source are realized, avoid the waste in being stirred to lithium source and part is mixed
Close non-uniform phenomenon；Material internal crystal defect prepared by Hydrothermal Synthesiss is small, reduces in sintering process due to the control of temperature
To the influence factor of material crystalline degree, calcining heat and the time of material are reduced, has saved cost；The preparation method of the present invention
So that positive electrode has higher discharge capacity and more excellent cycle performance.
The present invention realized by such technical scheme, Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material, by nickel cobalt manganese
Presoma and lithium source crystallize synthesis under cryogenic, and the positive electrode chemical formula is：LiNixCoyMnzMaO2, wherein, 0 ＜ x
0.9,0 ＜ y ＜ of ＜, 0.5,0 ＜ z ＜ 0.3,0 ＜ a ＜ 0.1, wherein M are Mg2+、Al3+、Ti4+、Nb5+Deng one kind of element compound
It is or a variety of；Comprise the following steps：
S1, by nickel salt, cobalt salt, manganese salt on request ratio be configured to nickeliferous, cobalt, manganese Metal cation mixed solution with
0.1%~0.2% salting liquid composition mixing salt solution A containing doped metallic elements M, prepares sodium hydroxide and ammoniacal liquor mixed base
Solution B；
S2, two kinds of solution of A, B are pumped into reactor simultaneously respectively by peristaltic pump and are stirred reaction, in course of reaction
It is 10.6~11.40 by pH on-line detector control materials pH；50~65 DEG C of reaction temperature, stirring, reaction obtain after terminating
Material is scrubbed, press filtration, the nickel cobalt manganese persursor material for being dried to obtain doping vario-property.
S3, nickel cobalt manganese presoma and lithium source are pressed into metal ratio 1:1~1:2 it is well mixed be placed in autoclave, add water
The 80% of reactor volume is dissolved to, in 160~250 DEG C of 20~30h of isothermal reaction.
S4, resulting material is dried, crush after be placed in Muffle furnace and sinter, 700~980 DEG C of Isothermal sinters 6~
16h, constant temperature are down to room temperature after terminating, and nickel cobalt manganese lithium anode material is obtained after crushing, sieving.
Further, nickel salt is at least one of nickel sulfate, nickel chloride or nickel nitrate in S1；Cobalt salt is cobaltous sulfate, chlorine
Change at least one of cobalt or cobalt nitrate；Manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate.
Further, lithium source is at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate in S3.
Further, mixing speed is 200~400 revs/min in S2.
Further, pH is 11.2 ± 0.2 in S2,55 DEG C of temperature.
Further, 190 DEG C of isothermal reaction 26h in S3 mesohighs reactor.
Further, it is to sinter 8h under 820 DEG C of constant temperature in S4.
Further, the heating rate of Muffle furnace is 2~6 DEG C in S4.
In the present invention, bulk phase-doped presoma and the synthesis of lithium source low-temperature hydrothermal will have been carried out, broken rear has been dried and carries out
The high temperature section sintering of lower temperature just can obtain that crystallinity is good, the uniform nickel-cobalt lithium manganate cathode material of particle diameter distribution, the party
Method shortens sintering time, reduce because repeatedly sintering and caused by crystal defect, avoid caused by during tradition is stirred
The problem of waste of lithium source and uneven local mixing；160~250 DEG C of 20~30h of isothermal reaction, hydro-thermal in autoclave simultaneously
Synthetic method reduces the volatilization of lithium source, and then reduces the excessive ratio of lithium source, reduces the residual of lithium；Hydro-thermal method is closed
Reaction in aqueous phase, alkali compounds caused by carbon dioxide reaction in lithium source and sintering atmosphere is reduced, thus reduced just
The alkali compounds on the surface of pole material, the energy density of lithium battery is improved, increase its cycle life.
By adopting the above-described technical solution, the present invention has the advantage that：By hydrothermal synthesis method, before realizing
Body and the low temperature crystallization of lithium source are driven, avoids the waste in being stirred to lithium source and local mixing non-uniform phenomenon；Hydro-thermal is closed
Material internal crystal defect into preparation is small, reduce in sintering process due to temperature influence of the control to material crystalline degree because
Element, calcining heat and the time of material are reduced, has saved cost；It is higher that the preparation method of the present invention make it that positive electrode has
Discharge capacity and more excellent cycle performance.
Brief description of the drawings
Fig. 1 is a kind of SEM schematic diagrames that the present invention prepares precursor of lithium ionic cell positive material.
Fig. 2 is that the present invention prepares a kind of SEM schematic diagrames of anode material for lithium-ion batteries intermediate steps.
Fig. 3 is that the present invention prepares a kind of SEM schematic diagrames after anode material for lithium-ion batteries sintering.
Fig. 4 is a kind of contrast schematic diagram of cycle performance curve that example 3 prepares anode material for lithium-ion batteries with comparative example.
Embodiment
Under the invention will be further described in conjunction with the accompanying drawings and embodiments.
Embodiment 1
S1, nickel sulfate 11.62Kg, cobaltous sulfate 4.48Kg, manganese sulfate 2.38Kg are pressed into Ni:Mn:Co mol ratios 6:2:2 prepare
Into 2mol/L sulfate liquor, take aluminum nitrate 0.063Kg to be added after dissolving and mixing salt solution A is formed in above-mentioned salting liquid；Again
The concentration of preparation sodium hydroxide and ammoniacal liquor is respectively 3.0mol/L, 0.45mol/L mixed ammonium/alkali solutions B；
S2, the mixing salt solution A and mixed ammonium/alkali solutions B prepared while it is pumped into reactor, control alkali lye B flow makes
The pH of mixed reaction solution is 10.8 ± 0.2 in reactor, and mixed solution mixing speed is 200 revs/min in reactor, reaction temperature
Spend for 65 DEG C, after coprecipitation reaction terminates, after the washing of obtained sediment, press filtration, drying, obtain doping type nickel-cobalt-manganese ternary
Presoma；
S3, by the nickel cobalt manganese presoma obtained in S2 and lithium hydroxide by nickel cobalt manganese total atom number and lithium atom number ratio 1:
1.06 uniformly mixing, add in autoclave, add water to the 80% of reactor volume and stir evenly together, in 160 DEG C of reactions
30h；
S4, reaction take out material after terminating, dry, crush after be placed in Muffle furnace and sinter, in oxygen atmosphere with 2 DEG C/
Min speed is warming up to 700 DEG C of Isothermal sinter 16h, and constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium is being obtained after crushing, sieving just
Pole material.
Embodiment 2
S1, nickel sulfate 11.62Kg, cobaltous sulfate 4.48Kg, manganese sulfate 2.38Kg are pressed into Ni:Mn:Co mol ratios 6:2:2 prepare
Into 2mol/L sulfate liquor, take aluminum nitrate 0.063Kg to be added after dissolving and mixing salt solution A is formed in above-mentioned salting liquid；Again
The concentration of preparation sodium hydroxide and ammoniacal liquor is respectively 3.0mol/L, 0.45mol/L mixed ammonium/alkali solutions B；
S2, the mixing salt solution A and mixed ammonium/alkali solutions B prepared while it is pumped into reactor, control alkali lye B flow makes
The pH of mixed reaction solution is 11.2 ± 0.2 in reactor, and mixed solution mixing speed is 400 revs/min in reactor, reaction temperature
Spend for 50 DEG C, after coprecipitation reaction terminates, after the washing of obtained sediment, press filtration, drying, obtain doping type nickel-cobalt-manganese ternary
Presoma；
S3, by the nickel cobalt manganese presoma obtained in S2 and lithium hydroxide by nickel cobalt manganese total atom number and lithium atom number ratio 1:1
Uniformly mixing, add together in autoclave, add water to the 80% of reactor volume and stir evenly, react 20h at 250 DEG C；
S4, reaction take out material after terminating, dry, crush after be placed in Muffle furnace and sinter, in oxygen atmosphere with 6 DEG C/
Min speed is warming up to 980 DEG C of Isothermal sinter 6h, and constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium positive pole is obtained after crushing, sieving
Material.
Embodiment 3
S1, nickel sulfate 11.62Kg, cobaltous sulfate 4.48Kg, manganese sulfate 2.38Kg are pressed into Ni:Mn:Co mol ratios 6:2:2 prepare
Into 2mol/L sulfate liquor, take aluminum nitrate 0.063Kg to be added after dissolving and mixing salt solution A is formed in above-mentioned salting liquid；Again
The concentration of preparation sodium hydroxide and ammoniacal liquor is respectively 3.0mol/L, 0.45mol/L mixed ammonium/alkali solutions B；
S2, the mixing salt solution A and mixed ammonium/alkali solutions B prepared while it is pumped into reactor, control alkali lye B flow makes
The pH of mixed reaction solution is 11.2 ± 0.2 in reactor, and mixed solution mixing speed is 400 revs/min in reactor, reaction temperature
Spend for 55 DEG C, after coprecipitation reaction terminates, after the washing of obtained sediment, press filtration, drying, obtain doping type nickel-cobalt-manganese ternary
Presoma；
S3, by the nickel cobalt manganese presoma obtained in S2 and lithium hydroxide by nickel cobalt manganese total atom number and lithium atom number ratio 1:2
Uniformly mixing, add together in autoclave, add water to the 80% of reactor volume and stir evenly, react 26h at 190 DEG C；
S4, reaction take out material, are placed in Muffle furnace and sinter after dry, crushing, with 3.5 in oxygen atmosphere after terminating
DEG C/min speed is warming up to 840 DEG C of Isothermal sinter 8h, constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium is obtained after crushing, sieving
Positive electrode.
Embodiment 4
S1, nickel sulfate 11.62Kg, cobaltous sulfate 4.48Kg, manganese sulfate 2.38Kg are pressed into Ni:Mn:Co mol ratios 6:2:2 prepare
Into 2mol/L sulfate liquor, a part of concentrated sulfuric acid regulation pH value of solution is added, takes magnesium nitrate 0.074Kg to be added after dissolving above-mentioned
Mixing salt solution A is formed in salting liquid；The concentration for preparing sodium hydroxide and ammoniacal liquor again is respectively the mixed of 4.0mol/L, 0.8mol/L
Close aqueous slkali B；,
S2, by the salting liquid A prepared and aqueous slkali B while it is pumped into reactor, control alkali lye B flow makes reactor
The pH of middle mixed reaction solution is 11.4, and mixed solution mixing speed is 400 revs/min in reactor, and reaction temperature is 55 DEG C, altogether
After precipitation reaction terminates, after the washing of obtained sediment, press filtration, drying, doping type nickel-cobalt-manganese ternary presoma is obtained；
S3, by obtained nickel cobalt manganese presoma and lithium hydroxide by nickel cobalt manganese total atom number and lithium atom number ratio 1:1.065
Uniformly mixing, add together in autoclave, add water to reactor volume 80% stirs evenly, and reacts 28h at 180 DEG C；
S4, reaction take out material after terminating, dry, crush after be placed in Muffle furnace and sinter, in oxygen atmosphere with 3 DEG C/
Min speed is warming up to 820 DEG C of Isothermal sinter 8h, and constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium positive pole is obtained after crushing, sieving
Material.
Comparative example
S1, nickel sulfate 11.62Kg, cobaltous sulfate 4.48Kg, manganese sulfate 2.38Kg are pressed into Ni:Mn:Co mol ratios 6:2:2 prepare
Into 2mol/L sulfate liquor, a part of concentrated sulfuric acid regulation pH value of solution is added, takes aluminum nitrate 0.063Kg to be added after dissolving above-mentioned
Mixing salt solution A is formed in salting liquid；The concentration for being reconfigured at sodium hydroxide and ammoniacal liquor is respectively 3.0mol/L, 0.45mol/L
Mixed ammonium/alkali solutions B；
S2, the salting liquid A and aqueous slkali B prepared by while it is pumped into reactor, control alkali lye B flow makes reaction
The pH of mixed reaction solution is 11.4 in kettle, and mixed solution mixing speed is 400 revs/min in reactor, and reaction temperature is 55 DEG C,
After coprecipitation reaction terminates, after the washing of obtained sediment, press filtration, drying, the nickel-cobalt-manganese ternary presoma of doping type is obtained；
S3, the presoma obtained by is with lithium carbonate by nickel cobalt manganese total atom number and lithium atom number ratio 1:1.065 at a high speed
Uniformly mixed in mixer；
S4, it is placed in Muffle furnace and sinters, 600 degree of Isothermal sinter 4h is risen to 3.5 DEG C/min speed in oxygen atmosphere；Again
880 DEG C of Isothermal sinter 10h are raised to, constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium anode material is obtained after crushing, sieving.
Battery performance test
Fig. 4 is in the present invention, embodiment 3 prepares the one of the positive electrode that anode material for lithium-ion batteries is prepared with comparative example
Kind circulation contrast schematic diagram.From fig. 4, it can be seen that the positive electrode that embodiment 3 is prepared by hydro-thermal reaction is used as lithium-ion electric
Pond positive electrode, positive electrode prepared by relative contrast's example mixed sintering, circulating battery is after 300 weeks, Hydrothermal Synthesiss material
Capability retention is 96%, and the material capacity conservation rate in comparative example 3 is 93%.Hydrothermal synthesis method has been obviously improved material
Cycle performance.
In addition, the positive electrode prepared to hydro-thermal method is scanned electron microscope (SEM) test；Fig. 1 is in the present invention
A kind of SEM schematic diagrames of the positive electrode material precursor of preparation, it can be seen that material spherical degree pattern is good, particle size
It is in mostly between 10~15 μm；Fig. 2 is a kind of SEM schematic diagrames that hydro-thermal method prepares positive electrode intermediate product；Fig. 3 is into one
A kind of SEM schematic diagrames for the positive electrode that step sintering obtains, it can be seen that second particle size distribution is uniform.
Embodiment and comparative example test data contrast table：
Comprehensive accompanying drawing and test data contrast table understand that hydro-thermal method prepares positive electrode compared with comparative example, present invention system
Preparation Method can be such that presoma is mixed with lithium source evenly, and reaction contact is abundant, and the material crystal formation prepared more completely is stablized,
So that stability of the material under big voltage is more preferable, positive electrode is set to be improved on capacity and cycle performance.
Claims (8)
1. a kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material, it is characterised in that by nickel cobalt manganese presoma and lithium
Source crystallizes synthesis under cryogenic, and the positive electrode chemical formula is：LiNixCoyMnzMaO2, wherein, the ＜ y of 0 ＜ x ＜ 0.9,0
0.5,0 ＜ z ＜ of ＜ 0.3,0 ＜ a ＜ 0.1, wherein M are Mg2+、Al3+、Ti4+、Nb5+The one or more of element compound；Including
Following steps：
S1, by nickel salt, cobalt salt, manganese salt on request ratio be configured to nickeliferous, cobalt, the mixed solution of manganese Metal cation and 0.1%~
The 0.2% salting liquid composition mixing salt solution A containing doped metallic elements M, prepares sodium hydroxide and ammoniacal liquor mixed ammonium/alkali solutions B；
S2, two kinds of solution of A, B are pumped into reactor simultaneously respectively by peristaltic pump and are stirred reaction, are passed through in course of reaction
PH on-line detector control materials pH is 10.6~11.40；50~65 DEG C of reaction temperature, stirring, the thing that reaction obtains after terminating
Expect scrubbed, press filtration, be dried to obtain the nickel cobalt manganese persursor material of doping vario-property；
S3, nickel cobalt manganese presoma and lithium source are pressed into metal ratio 1:1~1:2 it is well mixed be placed in autoclave, be dissolved in water to
The 80% of reactor volume, in 160~250 DEG C of 20~30h of isothermal reaction；
S4, resulting material is dried, crush after be placed in Muffle furnace and sinter, in 700~980 DEG C of 6~16h of Isothermal sinter,
Constant temperature is down to room temperature after terminating, and nickel cobalt manganese lithium anode material is obtained after crushing, sieving.
2. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S1
Nickel salt is at least one of nickel sulfate, nickel chloride or nickel nitrate；Cobalt salt is at least one in cobaltous sulfate, cobalt chloride or cobalt nitrate
Kind；Manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate.
3. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S3
Lithium source is at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate.
4. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S2
Mixing speed is 200~400 revs/min.
5. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S2
PH is 11.2 ± 0.2,55 DEG C of temperature.
6. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S3
190 DEG C of isothermal reaction 26h in autoclave.
7. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S4
To sinter 8h under 820 DEG C of constant temperature.
8. the preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that in S4
The heating rate of Muffle furnace is 2~6 DEG C.
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Cited By (5)
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| CN108376778A (en) * | 2018-02-27 | 2018-08-07 | 天津丹兴科技有限责任公司 | The method that solvent-thermal method prepares high-performance lithium-rich anode material |
| CN109052492A (en) * | 2018-07-24 | 2018-12-21 | 北京科技大学 | A method of tertiary cathode material is prepared by lateritic nickel ore leaching solution |
| CN112421013A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Preparation method of layered lithium manganate cathode material with low lithium-manganese ratio |
| CN112479261A (en) * | 2020-11-03 | 2021-03-12 | 北京科技大学 | Modification method for lithium-rich manganese-based material precursor through nickel sulfate solution hydrothermal treatment |
| CN113488644A (en) * | 2021-06-25 | 2021-10-08 | 万向一二三股份公司 | Preparation method of high-nickel ternary material and application of high-nickel ternary material in solid-state lithium ion battery positive plate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108376778A (en) * | 2018-02-27 | 2018-08-07 | 天津丹兴科技有限责任公司 | The method that solvent-thermal method prepares high-performance lithium-rich anode material |
| CN109052492A (en) * | 2018-07-24 | 2018-12-21 | 北京科技大学 | A method of tertiary cathode material is prepared by lateritic nickel ore leaching solution |
| WO2020019920A1 (en) * | 2018-07-24 | 2020-01-30 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
| CN112479261A (en) * | 2020-11-03 | 2021-03-12 | 北京科技大学 | Modification method for lithium-rich manganese-based material precursor through nickel sulfate solution hydrothermal treatment |
| CN112421013A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Preparation method of layered lithium manganate cathode material with low lithium-manganese ratio |
| CN113488644A (en) * | 2021-06-25 | 2021-10-08 | 万向一二三股份公司 | Preparation method of high-nickel ternary material and application of high-nickel ternary material in solid-state lithium ion battery positive plate |
| CN113488644B (en) * | 2021-06-25 | 2022-05-13 | 万向一二三股份公司 | Preparation method of high-nickel ternary material and application of high-nickel ternary material in solid-state lithium ion battery positive plate |
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