CN108110242A - A kind of preparation method of lithium ion battery nickel manganese cobalt composite material - Google Patents
A kind of preparation method of lithium ion battery nickel manganese cobalt composite material Download PDFInfo
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- CN108110242A CN108110242A CN201711376677.5A CN201711376677A CN108110242A CN 108110242 A CN108110242 A CN 108110242A CN 201711376677 A CN201711376677 A CN 201711376677A CN 108110242 A CN108110242 A CN 108110242A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium ion battery preparation methods of nickel manganese cobalt composite material, include the following steps：(1) lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, vanadium oxalate and yttrium nitrate are dissolved in the mixed solution of water；Mixed solution and mixed alkali liquor are sprayed into reactor, is atomized mixed solution, heats the lithium-nickel-manganese-cobalt presoma precipitation that must adulterate vanadium and yttrium；By the drying of presoma precipitation, briquetting, pre-sintering is burnt, and the Li-Ni-Mn-Co-O material for preparing doping vanadium and yttrium is made；(2) add in citric acid in the Li-Ni-Mn-Co-O material of doping vanadium and yttrium and the deionized water of mixed material can be submerged, ball milling, sintering obtain the lithium-nickel-manganese-cobalt O compoiste material that carbon coating adulterates vanadium and yttrium.Lithium ion battery prepared by present invention nickel manganese cobalt composite material, improves the high rate cyclic stability of material, improves its conductivity；When for lithium ion battery, there is higher electric conductivity and good cyclical stability.
Description
Technical field
The present invention relates to lithium ion battery manufacturing field more particularly to a kind of lithium ion battery nickel manganese cobalt composite materials
Preparation method.
Background technology
Lithium ion battery becomes the mainstream development direction of secondary cell with its outstanding performance, in new-energy automobile and big rule
Mould energy-storage system has huge growth potential, and positive electrode accounts for the 30%~40% of lithium ion manufacture cost, is to determine lithium
Ion battery safety, performance, cost and the critical material in service life
Commercial Li-ion battery uses LiCoO more2As positive electrode, but cobalt resource is in short supply, expensive and have
Poison, reversible specific capacity only have 140mAh/g or so.Therefore it is following lithium ion battery to find of fine quality, inexpensive anode alternative materials
The Main way of development.The study found that laminated Li-Ni-Mn cobalt positive electrode (abbreviation tertiary cathode material) has preferably had both cobalt
It is the advantages of sour lithium, lithium nickelate, LiMn2O4, preferable with height ratio capacity, stable cycle performance, advantage of lower cost, security performance
The features such as, it is considered to be for the ideal chose of mixed type power electric motor car (HEV), be also considered as it is best, can substitute
LiCoO2Positive electrode.Therefore, the research of the series material causes great attention.
New ternary compound oxides nickel manganese cobalt acid lithium is because of the advantages that cheap, it is easy to synthesize, and energy density is high, quilt
It is considered most possibly substitution commercialization at present LiCoO2Novel anode material and a big heat of Study on Li-ion batteries now
Point.But have a disadvantage in that it in high power charging-discharging, capacity attenuation is very fast, and high rate performance is bad.
The content of the invention
The present invention provides a kind of preparation method of lithium ion battery nickel manganese cobalt composite material, is prepared just using this method
Pole material, in the case of high power charging-discharging, still with good electrochemistry cycle performance.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of preparation method of lithium ion battery nickel manganese cobalt composite material, including
Following steps：
(1) the Li-Ni-Mn-Co-O material of doping vanadium and yttrium is prepared
Lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, vanadium oxalate and yttrium nitrate are pressed into metal ion molar ratio 3.05:1：1:
1：(0.02-0.03)：(0.005-0.01) is dissolved in the mixing for forming that concentration of metal ions is 3-5mol/L in water-organic solvent
Solution；
Prepare the mixed alkali liquor of ammonium hydrogen carbonate, hydrogen peroxide and acetone, the wherein concentration of ammonium hydrogen carbonate is 2-3mol/L, dioxygen
The concentration of water is 0.3-0.5mol/L, and the mixed solution and mixed alkali liquor are sprayed into reactor so that metallic solution and
Mixed alkali liquor is sufficiently mixed, and pH value is controlled then to be atomized mixed solution by compressed air, aerosol is directed to for 10-12
Quartz reactor heating obtains the lithium-nickel-manganese-cobalt presoma precipitation of doping vanadium and yttrium；
By the drying of presoma precipitation, briquetting, in air atmosphere, pre-sintering 3-4h is carried out at a temperature of 400-600 DEG C,
After sintered product cooling after grinding, sieving, continue to be sintered 12- at a temperature of 800-900 DEG C under oxygen atmosphere
The Li-Ni-Mn-Co-O material for preparing doping vanadium and yttrium is made in 15h；
(2) the Li-Ni-Mn-Co-O material of carbon coating doping vanadium and yttrium
The citric acid of 2-3wt% is added in the Li-Ni-Mn-Co-O material of above-mentioned doping vanadium and yttrium and mixture can be submerged
The deionized water of material is put into ball mill with the rotating speed ball milling 3-5h of 300-400r/min, is uniformly mixed, after drying, in air
It is sintered under atmosphere, is naturally cooling to after room temperature adulterate the lithium-nickel-manganese-cobalt O compoiste material of vanadium and yttrium to carbon coating.
Further, it is described preparation method of the lithium ion battery with nickel manganese cobalt composite material the step of in (1)
Lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, the metal ion molar ratio of vanadium oxalate and yttrium nitrate are 3.05:1：1:1：0.03：
0.008。
Further, preparation method of the lithium ion battery with nickel manganese cobalt composite material the step of in (1), step
(1) in, the organic solvent is ethylene glycol, and the mass ratio of water and ethylene glycol is 1:3-4.
Further, preparation method of the lithium ion battery with nickel manganese cobalt composite material the step of in (1), step
(1) in, the pre-sintering temperature is 500-530 DEG C, and sintering temperature is 840-860 DEG C.
Further, preparation method of the lithium ion battery with nickel manganese cobalt composite material the step of in (1), step
(2) in, the sintering process is：After being warming up to 600-700 DEG C with 5-10 DEG C/min heating rates keep the temperature 2-3 it is small when, then with
The heating rate of 10-15 DEG C/min is warming up to 900-1000 DEG C, keeps the temperature 4-5h, makes its carbonization, finally with the drop of 15-20 DEG C/min
Warm speed is down to 400-600 DEG C of annealing 5-10h.
It is compound with nickel manganese cobalt that the second aspect of the invention is to provide lithium ion battery prepared by a kind of described the method
Material.
The present invention compared with prior art, is had the following technical effect that using above-mentioned technical proposal：
Lithium ion battery prepared by present invention nickel manganese cobalt composite material employs wet method doping process, prepares doping vanadium
With the Li-Ni-Mn-Co-O material of rare earth element yttrium, to improve the high rate cyclic stability of material, and using machinery and it is carbonized
Technique is formed on its surface one layer of carbon coating layer, improves its conductivity, therefore the composite material has when for lithium ion battery
There are higher electric conductivity and good cyclical stability so that lithium ion battery has high specific capacity and longer use
Service life.
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
The preparation of embodiment 1 lithium ion battery nickel manganese cobalt composite material
(1) lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, vanadium oxalate and yttrium nitrate are pressed into metal ion molar ratio 3.05:
1：1:1：0.02：0.005 is dissolved in the mixed solution for forming that concentration of metal ions is 3mol/L in water-organic solvent, wherein, have
Solvent is ethylene glycol, and the mass ratio of water and ethylene glycol is 1:3.
Prepare the mixed alkali liquor of ammonium hydrogen carbonate, hydrogen peroxide and acetone, the wherein concentration of ammonium hydrogen carbonate is 2mol/L, hydrogen peroxide
Concentration for 0.3mol/L, the mixed solution and mixed alkali liquor are sprayed into reactor so that metallic solution and mixed base
Liquid is sufficiently mixed, and it is 10 to control pH value, is then atomized mixed solution by compressed air, aerosol is directed to quartz reactor
Heating obtains the lithium-nickel-manganese-cobalt presoma precipitation of doping vanadium and yttrium.
By the drying of presoma precipitation, briquetting, in air atmosphere, pre-sintering 4h, sintering are carried out at a temperature of 4000 DEG C
After product cooling after grinding, sieving, continue to be sintered 12h at a temperature of 800 DEG C under oxygen atmosphere, obtained preparation is mixed
The Li-Ni-Mn-Co-O material of miscellaneous vanadium and yttrium.
(2) citric acid of 2wt% is added in the Li-Ni-Mn-Co-O material of above-mentioned doping vanadium and yttrium and mixing can be submerged
The deionized water of material is put into ball mill with the rotating speed ball milling 5h of 300r/min, is uniformly mixed, after drying, in air atmosphere
Lower sintering when heat preservation 3 is small after being warming up to 600 DEG C with 5 DEG C/min heating rates, is then warming up to the heating rate of 10 DEG C/min
900 DEG C, 5h is kept the temperature, makes its carbonization, 600 DEG C of annealing 10h are finally down to the cooling rate of 15 DEG C/min, are naturally cooling to room temperature
Afterwards to get adulterating the lithium-nickel-manganese-cobalt O compoiste material of vanadium and yttrium to carbon coating.
The preparation of embodiment 2 lithium ion battery nickel manganese cobalt composite material
(1) lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, vanadium oxalate and yttrium nitrate are pressed into metal ion molar ratio 3.05:
1：1:1：0.03：0.01 is dissolved in the mixed solution for forming that concentration of metal ions is 5mol/L in water-organic solvent, wherein, have
Solvent is ethylene glycol, and the mass ratio of water and ethylene glycol is 1:4.
Prepare the mixed alkali liquor of ammonium hydrogen carbonate, hydrogen peroxide and acetone, the wherein concentration of ammonium hydrogen carbonate is 3mol/L, hydrogen peroxide
Concentration for 0.5mol/L, the mixed solution and mixed alkali liquor are sprayed into reactor so that metallic solution and mixed base
Liquid is sufficiently mixed, and it is 12 to control pH value, is then atomized mixed solution by compressed air, aerosol is directed to quartz reactor
Heating obtains the lithium-nickel-manganese-cobalt presoma precipitation of doping vanadium and yttrium.
By the drying of presoma precipitation, briquetting, in air atmosphere, pre-sintering 3h, sintering production are carried out at a temperature of 600 DEG C
After object cooling after grinding, sieving, continue under oxygen atmosphere, 12h is sintered at a temperature of 900 DEG C, obtained preparation is mixed
The Li-Ni-Mn-Co-O material of miscellaneous vanadium and yttrium.
(2) citric acid of 3wt% is added in the Li-Ni-Mn-Co-O material of above-mentioned doping vanadium and yttrium and mixing can be submerged
The deionized water of material is put into ball mill with the rotating speed ball milling 3h of 400r/min, is uniformly mixed, after drying, in air atmosphere
Lower sintering when heat preservation 2 is small after being warming up to 700 DEG C with 10 DEG C/min heating rates, is then heated up with the heating rate of 15 DEG C/min
To 1000 DEG C, 4h is kept the temperature, makes its carbonization, 400 DEG C of annealing 5h are finally down to the cooling rate of 20 DEG C/min, are naturally cooling to room
To get adulterating the lithium-nickel-manganese-cobalt O compoiste material of vanadium and yttrium to carbon coating after temperature.
Comparative example
(1) first, by cobaltous sulfate, nickel sulfate, manganese sulfate and carbon containing buffer in the ratio 0.1 of the amount of substance：0.16：
0.48：0.26 is configured to the solution A of 1mol/L, wherein carbon containing buffer be by after 1200 DEG C of calcinations of high temperature carbon, white granulated sugar,
HCl, deionized water according to the amount of substance ratio 90：5：1：4 mix；Ammonium hydroxide, the NaOH solution that concentration is 10% are pressed into body
Product ratio 1：4.48 are made into 2mol/L solution Bs.
It (2) will be by the qualified solution A of filtering, solution B by volume 1 with metering pump：1 is uniformly pumped into reaction kettle, sets
Device frequency：Revolution 20Hz, rotation 5Hz, room temperature at the uniform velocity stir 1H；Then, adjusting device frequency：Revolve round the sun 50Hz, rotation 30Hz,
It is to stir 4H at 45 DEG C in temperature, uniformly mixes, 9.7, product is intermediate M for pH value control；It is uniformly pumped with metering pump again
Enter with the NaOH solution that the concentration of the amount of the substances such as intermediate M is 10%, 10.1, generation liquid is intermediate for pH value control
N；Intermediate N quiescent setting 4H, separation of solid and liquid removes liquid, then by adjusting device frequency：It revolves round the sun 10Hz, rotation 5Hz, time
28min is reacted；Then it is slowly added to carbon containing buffer, the volume ratio of carbon containing sustained release agent and intermediate N are 1：5, equipment frequency
Rate is arranged to revolution 50Hz, rotation 30Hz, time 20H and is reacted, generation termination product X；Termination product X is washed through deionization
Wash 3 times, power be 3700W microwave drying, cross mesh number be the nonmetallic net filtration of 250 purposes, it is spare.
(3) weigh lithium carbonate and add in reaction kettle, the 1/ of the amount for the substance that the amount for adding in the substance of lithium carbonate is termination product X
2, lithium carbonate carries out dry-mixing grinding, time 2H with the termination product X after filtering in inert gas environment；By 250 mesh
After screen filtration, pre-sintering 2H is carried out at a temperature of 300 DEG C, the air inflow of inert gas is 10 cubes/second；At 920 DEG C
At a temperature of be sintered 18H, the air inflow of inert gas is 20 cubes/second；It crushes, crush finally by Hubei Province formula, screening out iron excessively,
Generating structure is Li (Co0.1Ni0.16Mn0.48C0.26) O2.
Above-described embodiment 1, embodiment 2 and comparative example products therefrom and conductive agent acetylene black, binding agent PVDF is (poly- inclined
Vinyl fluoride) according to mass ratio 93：3：4 are uniformly mixed, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone),
It being evenly applied on aluminium foil, is put into baking oven, 80-120 DEG C of drying 1h, taking-up is washed into pole piece, when 85 DEG C of vacuum drying 12 are small, into
Row tabletting, when 85 DEG C of vacuum drying 12 are small, obtained experimental cell pole piece.Using lithium piece as to electrode, electrolyte 1.5mol/L
EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution of LiPF6, membrane are celgard2400 films,
CR2025 type button cells are assembled into glove box full of argon gas atmosphere, charge and discharge are 3.6V by voltage.In test temperature
To carry out electric performance test at 25 DEG C, the material of the embodiment one and two is compared with the product of comparative example after tested, specific capacity
33-41% is improved, service life improves 1.5 times or more.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (6)
1. a kind of lithium ion battery preparation method of nickel manganese cobalt composite material, which is characterized in that include the following steps：
(1) the Li-Ni-Mn-Co-O material of doping vanadium and yttrium is prepared
Lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, vanadium oxalate and yttrium nitrate are pressed into metal ion molar ratio 3.05:1：1:1：
(0.02-0.03)：It is molten that (0.005-0.01) is dissolved in the mixing that formation concentration of metal ions is 3-5mol/L in water-organic solvent
Liquid；
The mixed alkali liquor of ammonium hydrogen carbonate, hydrogen peroxide and acetone is prepared, the wherein concentration of ammonium hydrogen carbonate is 2-3mol/L, hydrogen peroxide
Concentration is 0.3-0.5mol/L, the mixed solution and mixed alkali liquor is sprayed into reactor so that metallic solution and mixing
Lye is sufficiently mixed, and pH value is controlled then to be atomized mixed solution by compressed air, aerosol is directed to quartz for 10-12
Reactor heating obtains the lithium-nickel-manganese-cobalt presoma precipitation of doping vanadium and yttrium；
By the drying of presoma precipitation, briquetting, in air atmosphere, pre-sintering 3-4h, sintering are carried out at a temperature of 400-600 DEG C
After product cooling after grinding, sieving, continue to be sintered 12-15h at a temperature of 800-900 DEG C under oxygen atmosphere, make
The Li-Ni-Mn-Co-O material of doping vanadium and yttrium must be prepared；
(2) the Li-Ni-Mn-Co-O material of carbon coating doping vanadium and yttrium
The citric acid of 2-3wt% is added in the Li-Ni-Mn-Co-O material of above-mentioned doping vanadium and yttrium and mixed material can be submerged
Deionized water is put into ball mill with the rotating speed ball milling 3-5h of 300-400r/min, is uniformly mixed, after drying, in air atmosphere
Lower sintering is naturally cooling to after room temperature adulterate the lithium-nickel-manganese-cobalt O compoiste material of vanadium and yttrium to carbon coating.
2. the lithium ion battery according to claim 1 preparation method of nickel manganese cobalt composite material, which is characterized in that step
(1) in, the lithium chloride, nickel sulfate, manganese nitrate, cobalt chloride, the metal ion molar ratio of vanadium oxalate and yttrium nitrate are 3.05:1：
1:1：0.03：0.008.
3. the lithium ion battery according to claim 1 preparation method of nickel manganese cobalt composite material, which is characterized in that step
(1) in, the organic solvent is ethylene glycol, and the mass ratio of water and ethylene glycol is 1:3-4.
4. the lithium ion battery according to claim 1 preparation method of nickel manganese cobalt composite material, which is characterized in that step
(1) in, the pre-sintering temperature is 500-530 DEG C, and sintering temperature is 840-860 DEG C.
5. the lithium ion battery according to claim 1 preparation method of nickel manganese cobalt composite material, which is characterized in that step
(2) in, the sintering process is：After being warming up to 600-700 DEG C with 5-10 DEG C/min heating rates keep the temperature 2-3 it is small when, then with
The heating rate of 10-15 DEG C/min is warming up to 900-1000 DEG C, keeps the temperature 4-5h, makes its carbonization, finally with the drop of 15-20 DEG C/min
Warm speed is down to 400-600 DEG C of annealing 5-10h.
6. a kind of lithium ion battery nickel manganese cobalt composite material prepared such as any one of claim 1-5 the method.
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Cited By (4)
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| CN110336004A (en) * | 2019-06-28 | 2019-10-15 | 佛山科学技术学院 | A kind of nickelic positive electrode and preparation method thereof, lithium ion battery |
| CN110943212A (en) * | 2019-11-30 | 2020-03-31 | 华友新能源科技（衢州）有限公司 | Vanadium-doped nickel-manganese composite hydroxide and preparation method thereof |
| CN115710022A (en) * | 2022-11-17 | 2023-02-24 | 科立鑫(珠海)新能源有限公司 | Preparation method of high-density cobalt carbonate |
| CN116747757A (en) * | 2023-08-17 | 2023-09-15 | 新乡市弘力电源科技有限公司 | Pretreatment equipment for monocrystal high-nickel ternary material |
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