CN110224114A - A kind of anode material for lithium ion battery and preparation method thereof - Google Patents

A kind of anode material for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN110224114A
CN110224114A CN201810170541.7A CN201810170541A CN110224114A CN 110224114 A CN110224114 A CN 110224114A CN 201810170541 A CN201810170541 A CN 201810170541A CN 110224114 A CN110224114 A CN 110224114A
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lithium
positive electrode
lithium ion
ion battery
anode material
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张和宝
王岑
李喆
陆玉婷
叶兰
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Ann Price (nanjing) Co Ltd
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Ann Price (nanjing) Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 present invention relates to a kind of anode material for lithium ion battery and preparation method thereof, the molecular formula of the positive electrode is Li6+aCo1‑ xMxO4‑b, wherein M is doped chemical, 0≤x≤0.1, -0.2≤a≤0.2, -0.2≤b≤0.2；The positive electrode specific capacity is higher, is obviously improved effect to the energy density of prepared battery, and the positive electrode surface can also there is certain coating to verify it is protected, have no adverse effects to battery following cycle.Positive electrode prepared by the present invention is used for lithium ion battery, shows the advantage that capacity is high, expansion is small, has recycled, the method for the present invention technical process is simple, is easy to realize industrial production.

Description

A kind of anode material for lithium ion battery and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of anode material for lithium ion battery and its preparation Method.
Background technique
Lithium ion battery since the advent of the world receives the extensive concern of people, and nowadays, lithium ion battery is widely used in Consumer electronics field and electric car industry.Meanwhile with the development of the society, requirement of the people to lithium ion battery increasingly The lithium ion battery energy density of height, instantly market application is lower, limits the continuation of the journey of consumption electronic product and electric car.Make For the important component of lithium ion battery, positive and negative pole material is the key that improve battery energy density.Cathode mainly uses day Right graphite, artificial graphite, hard carbon, soft carbon and silicon carbon material, graphite negative electrodes material is already close to its theoretical capacity (372mAh/ G) the upper limit, and silicon carbon material due to dilation biggish in cyclic process cause material dusting inactivate, simultaneously because expansion It is caused to repeatedly generate SEI and excessively consume lithium ion so that its cycle performance is poor, therefore is difficult only to pass through cathode at this stage Increase substantially the energy density of battery.Therefore the energy density that battery is improved by positive electrode seems extremely urgent.
LiCoO2As the common positive electrode of consumer electronics, theoretical capacity 274mAh/g, due to factors Limitation, in high voltage (4.4V vs.Li/Li+) under, LiCoO2Play capacity about 190mAh/g.It is filled using size particles Method, improve anode compacted density, by playing LiCoO under this maximum conditions2Capacity, reduce anode volume, LiCoO2The battery volume energy density of anode preparation is still difficult have breakthrough.LiFePO4It is common as power battery Positive electrode has the characteristics that stable structure and chemical stabilization, has preferable cycle performance in battery system.But LiFePO4Electronic conductivity low (10-9~10-10S/cm) and lithium ion spreads slow (1.8*10-14cm2/ s), while its specific volume Lower (140mAh/g) is measured, causes its gravimetric energy density relatively low.And ternary material (NCM, NCA) is by properly increasing transition gold The doping for belonging to element improves capacity performance to a certain extent, but due to the limitation of theoretical capacity, and energy density is also very Difficulty has the promotion of larger amplitude, while also bringing security risk.Therefore, it is attempted to improve the energy of battery by various methods Density, including improving the compacted density of material, the voltage for improving positive electrode, conductivity, carrying out transition metal to positive electrode The doping etc. of element, but the energy density of battery is still without qualitative leap.
103746114 A of Chinese patent CN discloses a kind of preparation method of lithium cobaltate cathode.The patent is using control knot Brilliant method, has been made specific cobaltosic oxide material, is produced using cobalt acid lithium prepared by this specific cobaltosic oxide material Product, powder particle is large, medium and small to be evenly distributed, and the compacted density of product is significantly improved.Simultaneously using nontransition metal at it Surface is coated, and the lithium cobaltate cathode after cladding reduces its reactivity with electrolyte, improves the cyclicity of battery Energy.But it is only 175mAh/g that the lithium cobaltate cathode material capacity, which plays, the energy density of battery is difficult have biggish mention It is high.
103730657 A of Chinese patent CN discloses a kind of preparation side of lithium phosphate/carbon-coated lithium iron phosphate composite Method.The patent is first fired into the LiFePO 4 material of uncoated carbon, next joined lithium phosphate and carbon in secondary mixing, burns Produce carbon-coated composite ferric lithium phosphate material.This method realizes the controllable of LiFePO 4 material partial size, separately by a pre-burning On the one hand, by secondary addition lithium phosphate and carbon, lithium phosphate and carbon being uniformly distributed on LiFePO4 surface are realized, it is final to make It is standby to have provided high conductivity and high performance carbon composite ferric lithium phosphate material.Material electric conductivity > 10-8S/cm, lithium ion diffusion Coefficient > 1.8*10-12cm2/s.At room temperature 0.2C, the discharge capacity of the material is 159mAh/g, under -20 DEG C of 0.2C of low temperature, Discharge capacity 117mAh/g.Although the patent improves LiFePO to a certain extent4Cryogenic property, but due to its capacity It limits, battery energy density made of the material is still lower.
At this stage, LiCoO2、LiFePO4, NCA, NCM etc. as positive electrode be applied to existing battery system, due in fact Border specific capacity still reaches to cause battery system volume or weight energy density lower, therefore develop one less than its theoretical capacity Money can really play the problem of positive electrode of high capacity is current urgent need to resolve.
Summary of the invention
The present invention provides a kind of anode material for lithium ion battery with height ratio capacity, and positive electrode collocation is existing just Polar body system, for shown in lithium-ion battery system energy density is high, expansion is small, have extended cycle life the advantages of.
To achieve the above object, present invention provide the technical scheme that
A kind of anode material for lithium ion battery, the molecular formula of the positive electrode are Li6+aCo1-xMxO4-b, wherein M is to mix Miscellaneous element, 0≤x≤0.1, -0.2≤a≤0.2, -0.2≤b≤0.2；The positive electrode spreads out using caused by X-ray diffraction Penetrating peak is Standard Symmetric Multivariate peak shape, the 2 θ angles of diffraction 31.3 ± 0.2 °, 31.8 ± 0.2 °, 32.5 ± 0.2 °, 32.7 ± 0.2 °, Equal salt free ligands peak, the above-mentioned angle of diffraction are respectively Co at 35.0 ± 0.2 °, 37.4 ± 0.2 °, 42.4 ± 0.2 °3O4、Li2CO3、 LiOH、Co(OH)2、Li2O2、LiCoO2With characteristic peak corresponding to CoO, prepared positive electrode is free of other any impurities, table It is now single homogeneous.Wherein Co and Li are uniformly distributed, and are observed under scanning electron microscope backscatter mode, material surface color It is uniform, the difference of no light and shade contrast, while the positive electrode surface is mellow and full, smooth.
Wherein, M is one of doped chemical Al, Mg, Ti, Zr, Si, Zn, Mn, Ni, Sn or a variety of.
The D50 of the positive electrode is between 3~15 μm, it is preferable that the D50 of the positive electrode is between 5~12 μm.
The particle diameter distribution width ((D90-D10)/D50) of the positive electrode is between 1.5~2.6.The D90, D50, D10 respectively indicate the partial size that cumulative particle sizes percentile reaches corresponding when 90%, 50%, 10%.
The particle size distribution of the positive electrode is uniform, while material surface is mellow and full, smooth, and electrode Shi Yifang is being made Face improves intergranular contact, on the other hand realizes the maximum compacted density of electrode.Simultaneously positive electrode size distribution compared with Narrow, when blending with other positive electrodes, large, medium and small even particle distribution is conducive to the compacted density for improving blend material.
The positive electrode surface has cladding substance, and the cladding substance is Al2O3、TiO2、SiO2、MgO、ZrO2、 AlF3、AlPO4、ZnO、SnO2, one of AlOOH or a variety of, the covering amount of the cladding substance is 0.1wt%~5wt%.
The positive electrode is higher than 850mAh/g for the specific discharge capacity in lithium ion battery.
By carrying out element doping to material, metal-doped element is replaced by vacancy, and electronic conductance not only can be improved And ionic conductance, improve high-multiplying power discharge when cycle efficieny and thermal stability, improve capacity, increase power, simultaneously because first The doping of element, inhibits the dissolution of cobalt atom in positive electrode, effectively so as to improve the stability of material.
Substance will be coated by cladding process and be evenly coated at the surface of material, the clad have inhibit positive electrode with The effect of moisture in air reaction, while the side reaction of positive electrode and electrolyte can also be effectively reduced, it significantly improves just The stability of pole material.
The present invention also announces the preparation method of above-mentioned anode material for lithium ion battery, it is characterised in that: including following Step:
(1) lithium presoma and cobalt precursor are subjected to ground and mixed according to a certain percentage, the presoma for obtaining lithium and cobalt is mixed Close object；Alternatively, lithium presoma and cobalt precursor are mixed according to a certain percentage, while a certain amount of doped chemical is added, Three's ground and mixed under low-humidity environment is uniform, obtains the presoma of lithium and cobalt and the mixture of doped chemical；
(2) high temperature sintering is carried out under non-oxidizing atmosphere to mixture obtained by step (1), obtains the first product；
(3) it is crushed, is sieved and is removed magnetic to the first product obtained by step (2), the positive electrode is made；Or by step (2) the first product of gained carries out the following processing: carrying out breakdown products after being crushed under low-humidity environment to the first product Cladding, or the first product is carried out to mix cladding under low-humidity environment with pre-coated object, the second product is obtained, second is produced Object carries out high temperature sintering under non-oxidizing atmosphere, is then crushed, sieves and removes magnetic, the positive electrode is made.
In step (1): the Li/Co ratio of the lithium presoma and cobalt precursor controls between 6.0~6.6；
The lithium presoma is lithium hydroxide, a hydronium(ion) lithia, lithium carbonate, lithium peroxide, lithia, lithium hydride One of or it is a variety of；
The cobalt precursor is one of cobaltosic oxide, cobalt protoxide, hydroxide cobalt or a variety of；
The lapping mode is mechanical lapping, preferably wet process and dry grinding, and the mechanical lapping uses high-speed stirred Any one in mill, ball mill, tube mill, type taper grinder, rod mill and sand mill；
The low humidity atmosphere be in the air of < 10% humidity, nitrogen, argon gas, helium, neon or Krypton atmosphere extremely Few one kind.
Mechanical lapping is carried out by above-mentioned technique, lithium presoma is first crushed to Nano grade, then realize with cobalt precursor It is sufficiently mixed.Lithium presoma is since partial size is larger, and for D99 up to 50~60 μm, the cobalt precursor being difficult with D99 less than 10 μm is real Now uniformly mixing.If when both be not mixed thoroughly, when sintering at high temperature, the lithium cobalt ratio of products therefrom is not according to setting Meter combination, but there are the mix products of different lithium cobalt ratio, are non-homogeneous phase so as to cause product, further result in its specific capacity It reduces, simultaneously because local lithium is excessive, alkalinity is higher, is unfavorable for being processed into for lithium battery anode.
In step (2): the temperature of the high temperature sintering is 400~1000 DEG C, and the time is 4~24 hours；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, helium, neon, hydrogen or krypton Gas.
In step (3), the crumbling method is mechanical lapping, and mechanical lapping is using high-speed stirred mill, ball mill, pipe mill Any one in machine, type taper grinder, rod mill and sand mill.
The cladding mode uses mechanical fusion or mechanical lapping mode, and the low humidity atmosphere in process of lapping is < 10% At least one of air, nitrogen, argon gas, helium, neon or Krypton atmosphere of humidity；
For the high temperature sintering temperature between 400~900 DEG C, the time is 2~12 hours；
Non-oxidizing atmosphere is provided by following at least one gases in the high-temperature sintering process: nitrogen, argon gas, helium, Neon or Krypton.
Compared with prior art, the beneficial effects of the present invention are:
1. positive electrode peak capacity prepared by reaches 977mAh/g, almost consistent with theoretical capacity；Prepared by simultaneously just Pole material
Material is stringent homogeneous phase, and there is no rich lithium or rich cobalt phases, not will lead to the part analysis lithium of cathode；
2. the pH value of positive electrode prepared by is lower, ensure that the subsequent machinability of material；
3. positive electrode prepared by pair carries out element doping and surface cladding, prepared positive electrode is improved in high magnification When electric discharge
Cycle efficieny and thermal stability, it is suppressed that the dissolution of cobalt atom in positive electrode, prepared positive electrode it is steady It is qualitative big
It is big to improve；
Positive electrode particle diameter distribution prepared by 4. than more uniform, can maximize improve electrode compacted density, when with its Its anode
When material blends, large, medium and small even particle distribution greatly improves the compacted density of electrode.In existing cell body System
In, greatly improve the energy density of battery；
5. preparation according to the present invention, doping, method for coating, simple process, Yi Shixian industrial production.
Detailed description of the invention
Fig. 1,2 are scanning electron microscope (SEM) photo under positive electrode secondary electron mode prepared by embodiment 1.
Fig. 3 is the SEM photograph under positive electrode backscatter mode prepared by embodiment 1.
Fig. 4 is X-ray diffraction (XRD) map of positive electrode prepared by embodiment 1.
Fig. 5,6 are the SEM photograph under positive electrode secondary electron mode prepared by embodiment 2.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
Weigh Li2O 89.64g, using rod mill by Li2O grinding is broken, and CoO 74.9g is added, continues to use rod mill Ground and mixed obtains uniformly mixed Li2The mixture of O and CoO.Resulting material is put into electrothermal furnace under argon atmosphere 400 DEG C of constant temperature are for 24 hours.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 14.1 μm of lithium ion batteries With positive electrode (Li6CoO4)。
It is characterized using anode material for lithium ion battery of the following equipment to above-mentioned preparation, following embodiment is all made of Identical characterization equipment.
Prepared positive electrode (Li is tested using 2000 type laser particle analyzer of Dandong Bai Te BetterSize6CoO4) grain Diameter distribution.
Prepared positive electrode (Li is observed using Hitachi SU8010 type scanning electron microscope6CoO4) surface shape Looks.Fig. 1 and Fig. 2 is respectively the SEM photograph under positive electrode secondary electron mode prepared by embodiment 1.Fig. 3 is 1 institute of embodiment Prepare the SEM photograph under positive electrode backscatter mode.As can be seen that prepared material is either in ruler from the above photo It is all very uniform in very little upper or surface-element distribution.
Using Rigaku MiniFlex600 type x-ray diffractometer, 10~80 ° of angle of diffraction of setting is 0.02 ° of step-length, fast 1 °/min of rate tests prepared positive electrode (Li under this parameter6CoO4) crystalline structure.
If the XRD spectrum of Fig. 4 is shown, prepared positive electrode crystal form and Li6CoO4It corresponds to well.Its 2 θ spreads out simultaneously Firing angle is in 31.3 ± 0.2 °, 31.8 ± 0.2 °, 32.5 ± 0.2 °, 32.7 ± 0.2 °, 35.0 ± 0.2 °, 37.4 ± 0.2 °, 42.4 Equal salt free ligands peak, the above-mentioned angle of diffraction are respectively Co at ± 0.2 °3O4、Li2CO3、LiOH、Co(OH)2、Li2O2、LiCoO2With CoO institute Corresponding characteristic peak shows prepared positive electrode without any Co, Li simple substance or compound impurities.
By obtained positive electrode (Li6CoO4), conductive agent and binder be added according to the ratio of 90:7:3 it is a certain amount of molten Agent is uniformly mixed, and is coated on aluminium foil, pure electrode is made.By obtained anode pole piece by cutting, vacuum bakeout and pairing Negative electrode tab and after diaphragm is wound together and puts into plastic-aluminum shell of corresponding size, inject a certain amount of electrolyte and seal, A complete lithium ion full battery can be obtained.Battery capacity is tested using new prestige test equipment BTS79, charging capacity can Up to 857mAh/g.
By obtained positive electrode (Li6CoO4)、LiCoO2, conductive agent and binder according to 4:94.4:0.6:1 ratio A certain amount of solvent is added to be uniformly mixed, is coated on aluminium foil, blending electrode is made and assembles full battery, tests electrochemistry Energy.The battery initial charge capacity reaches 217.1mAh/g, and energy density reaches 799Wh/L, and battery is followed by 500 charge and discharge After ring, capacity retention ratio 86.7%.
Following embodiment, which is all made of, is made pure electrode full battery and blending electrode full battery with the identical method of embodiment 1, Simultaneously according to positive corresponding adjustment cathode formula and surface density, and test in identical equipment two kinds of full battery charge/discharge capacities, Energy density and circulation conservation rate.
Embodiment 2
Weigh Li2Ball milling pearl is added by ratio of grinding media to material 4:1 in O 508.0g, LiH 16.0g, using ball mill grinding 30min, Co is then added3O4476.8g, MgO 2.4g, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, continue ball milling 30min, obtains Uniformly mixed Li2O、LiH、Co3O4With the mixture of MgO.Resulting material is put into electrothermal furnace under argon atmosphere 700 DEG C Constant temperature 20h.The first product is obtained after natural cooling, is put into ball mill after the first product is crushed, while weighing Al2O3 1.0g Ball grinder is added.Ball milling pearl, ball milling 20min is added according to ratio of grinding media to material 6:1.Resulting material is put into electrothermal furnace in argon atmosphere Lower 400 DEG C of constant temperature 12h.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 12.5 μm of lithium-ion electrics Pond positive electrode (Li6Co0.99Mg0.01O4).Fig. 5 and Fig. 6 is respectively positive electrode secondary electron mode prepared by embodiment 2 Under SEM photograph.Particle size distribution is more average as can be observed from Figure, and particle surface is relatively smooth.
The charging capacity of electrode prepared by the positive electrode is tested up to 913mAh/g.
By obtained positive electrode (Li6Co0.99Mg0.01O4)、LiCoO2, conductive agent and binder be according to 8:90.4:0.6:1 Ratio a certain amount of solvent be added be uniformly mixed, be coated on aluminium foil, blending electrode be made and assembles full battery, test electrification Learn performance.Positive charging capacity 248.8mAh/g, energy density reach 786Wh/L to the battery for the first time, and battery passes through 500 charge and discharges After electricity circulation, capacity retention ratio 85.3%.
Embodiment 3
LiOH 143.6g is weighed, LiOH is ground to broken, addition Co (OH) using Ball-stirring mill291.1g being separately added into The Al of 0.55g2O3With the NiO of 0.75g, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, continues to use Ball-stirring mill grinding, obtain Uniformly mixed LiOH, Co (OH)2、Al2O3With the mixture of NiO.Resulting material is put into electrothermal furnace under argon atmosphere 700 DEG C of constant temperature 20h.The first product is obtained after natural cooling, is put into ball mill after the first product is crushed, according to the ball of 6:1 Material is than addition ball milling pearl, ball milling 20min, then weighs MgO 0.2g and be added in ball grinder, ball milling 10min.The material that will be mixed 600 DEG C of constant temperature 4h under argon atmosphere are put into electrothermal furnace.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain intermediate value grain Diameter D50 is 12.3 μm of anode material for lithium ion battery (Li6Co0.98Al0.01Ni0.01O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 970mAh/g.
By obtained positive electrode (Li6Co0.98Al0.01Ni0.01O4)、LiCoO2, conductive agent and binder be according to 4:94.4: The ratio of 0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full battery, surveys Try chemical property.The battery initial charge capacity reaches 221.7mAh/g, and energy density reaches 801Wh/L, and battery passes through 500 After secondary charge and discharge cycles, capacity retention ratio 87.4%.
Embodiment 4
Weigh Li2CO3450.7g is added ball milling pearl by ratio of grinding media to material 4:1 and Co is then added using ball mill grinding 30min (OH)2176.6g, ZrO212.3g, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, continue to grind 30min, it is equal to obtain mixing Even Li2CO3、Co(OH)2And ZrO2Mixture.Resulting material is put into electrothermal furnace 1000 DEG C of constant temperature under argon atmosphere 10h.The first product is obtained after natural cooling, and the first product is crushed to after certain size and is put into fusion machine, is weighed simultaneously Al2O3And TiO2Fusion machine is added in each 6.4g, leads to nitrogen, keeps inert atmosphere in fusion machine cavity body, merges the linear speed of machine agitating paddle Degree is 24m/s, fusion treatment 30min.Material is put into electrothermal furnace 500 DEG C of constant temperature 12h under argon atmosphere.Freely it is cooled to It is taken out after room temperature, grind and is sieved to obtain median particle diameter D50 to be 10.3 μm of anode material for lithium ion battery (Li6Co0.95Zr0.05O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 946mAh/g.
By obtained positive electrode (Li6Co0.95Zr0.05O4)、LiCoO2, conductive agent and binder be according to 5:93.4:0.6:1 Ratio a certain amount of solvent be added be uniformly mixed, be coated on aluminium foil, blending electrode be made and assembles full battery, test electrification Learn performance.The battery initial charge capacity reaches 228.4mAh/g, and energy density reaches 792Wh/L, and battery passes through 500 charge and discharges After electricity circulation, capacity retention ratio 86.9%.
Embodiment 5
Weigh Li2CO3Ball milling pearl is added by ratio of grinding media to material 4:1 in 229.1g, and using ball mill grinding 30min, CoO is added 72.7g is separately added into 0.77g TiO2、0.55g Al2O3With 0.81g ZnO, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, Using ball mill grinding 30min, uniformly mixed Li is obtained2CO3、CoO、TiO2、Al2O3With the mixture of ZnO.By resulting material 1000 DEG C of constant temperature 10h under argon atmosphere are put into electrothermal furnace.The first product is obtained after natural cooling, after the first product is crushed It is put into ball mill, ball milling pearl, ball milling 20min is added according to the ratio of grinding media to material of 6:1, then weigh ZrO2、AlF3And SnO2Each 3.1g adds Enter in ball grinder, ball milling 10min.The material mixed is put into electrothermal furnace 700 DEG C of constant temperature 4h under argon atmosphere.Freely drop It is taken out after warming to room temperature, grind and is sieved to obtain median particle diameter D50 to be 7.2 μm of anode material for lithium ion battery (Li6Co0.97Ti0.01Al0.01Zn0.01O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 953mAh/g.
By obtained positive electrode (Li6Co0.97Ti0.01Al0.01Zn0.01O4)、LiCoO2, conductive agent and binder according to The ratio of 0.5:97.9:0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles Full battery tests chemical property.The battery initial charge capacity reaches 193.9mAh/g, and energy density reaches 746Wh/L, electricity Pond is after 500 charge and discharge cycles, capacity retention ratio 90.2%.
Embodiment 6
Weigh Li2O2Ball milling pearl is added by ratio of grinding media to material 4:1 in 559.7g, and ball mill grinding 30min is separately added into CoO148.4g、Co(OH)2184.0g weighs 1.1g Al respectively2O3With 1.2g SiO2, it is added in ball grinder, while pressing ball material Corresponding ball milling pearl is supplemented than 4:1, ball milling 30min obtains uniformly mixed Li2O2、CoO、Al2O3And SiO2Mixture.By institute It obtains material and is put into electrothermal furnace 750 DEG C of constant temperature 15h under argon atmosphere.The first product is obtained after natural cooling, by the first product It is put into fusion machine after being crushed to certain size, while weighing AlPO4Fusion machine is added in 8.9g, leads to nitrogen, keeps fusion machine cavity Internal inert atmosphere, the linear velocity of fusion machine agitating paddle are 24m/s, merge 30min.Material is put into electrothermal furnace in argon atmospher Enclose lower 650 DEG C of constant temperature 2h.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 9.6 μm of lithium-ion electrics Pond positive electrode (Li6Co0.99Al0.005Si0.005O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 965mAh/g.
By obtained positive electrode (Li6Co0.99Al0.005Si0.005O4)、LiCoO2, conductive agent and binder be according to 8: The ratio of 90.4:0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full electricity Chemical property is tested in pond.The battery initial charge capacity reaches 253.0mAh/g, and energy density reaches 787Wh/L, battery warp After crossing 500 charge and discharge cycles, capacity retention ratio 85.8%.
Embodiment 7
Weigh Li2O 185.3g, using rod mill by Li2O grinding is broken, and CoO 148.4g is added, is separately added into 0.81g ZnO and 0.83g MnO2, rod mill ground and mixed is continued to use, uniformly mixed Li is obtained2O, CoO, ZnO and MnO2It is mixed Close object.Resulting material is put into electrothermal furnace under argon atmosphere 400 DEG C of constant temperature for 24 hours.The first product is obtained after natural cooling, it will It is put into ball mill after first product is broken, ball milling pearl, ball milling 20min is added according to the ratio of grinding media to material of 6:1, then weigh 6.7g TiO2It is added in ball grinder, ball milling 10min.The material mixed is put into electrothermal furnace 500 DEG C of constant temperature 6h under argon atmosphere. It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 7.8 μm of anode material for lithium ion battery (Li6Co0.99Zn0.005Mn0.005O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 977mAh/g.
By obtained positive electrode (Li6Co0.99Zn0.005Mn0.005O4)、LiCoO2, conductive agent and binder be according to 4: The ratio of 94.4:0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full electricity Chemical property is tested in pond.The battery initial charge capacity reaches 222.0mAh/g, and energy density reaches 801Wh/L, battery warp After crossing 500 charge and discharge cycles, capacity retention ratio 87.9%.
Embodiment 8
Weigh Li2Ball milling pearl is added by ratio of grinding media to material 4:1 in O 558.8g, LiH 17.6g, using ball mill grinding 30min, Co is added3O4472.0g weighs 6.1g Al2O3, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, ball milling 30min is mixed Close uniform Li2O、LiH、Co3O4And Al2O3Mixture.Resulting material is put into electrothermal furnace 900 DEG C of perseverances under argon atmosphere Warm 12h.The first product is obtained after natural cooling, is put into ball mill after the first product is crushed, while weighing 17.5g's respectively ZnO, MgO and Al2O3, ball milling pearl is added according to the ratio of grinding media to material of 6:1, the material mixed is put into electrothermal furnace by ball milling 20min 700 DEG C of constant temperature 4h under argon atmosphere.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 3.4 μm Anode material for lithium ion battery (Li6.05Co0.98Al0.02O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 955mAh/g.
By obtained positive electrode (Li6.05Co0.98Al0.02O4)、LiCoO2, conductive agent and binder be according to 1.2:97.2: The ratio of 0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full battery, surveys Try chemical property.The battery initial charge capacity reaches 199.3mAh/g, and energy density reaches 774Wh/L, and battery passes through 500 After secondary charge and discharge cycles, capacity retention ratio 89.3%.
Embodiment 9
Weigh Li2CO3Ball milling pearl is added by ratio of grinding media to material 4:1 in 458.1g, and using ball mill grinding 30min, Co is added (OH)2184.9g weighs 1.53g SnO2, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, continue ball milling 30min, is mixed Close uniform Li2CO3、Co(OH)2And SnO2Mixture.Resulting material is put into electrothermal furnace 600 DEG C of perseverances under argon atmosphere Warm 14h.The first product is obtained after natural cooling, is put into ball mill after the first product is crushed, while weighing 6.5g's respectively ZnO and Al2O3, ball milling pearl is added according to the ratio of grinding media to material of 6:1, the material mixed is put into electrothermal furnace in argon by ball milling 20min Atmosphere encloses lower 600 DEG C of constant temperature 2h.Taken out after being freely cooled to room temperature, grind and be sieved to obtain median particle diameter D50 be 6.8 μm of lithiums from Sub- positive electrode for battery material (Li6Co0.995Sn0.005O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 896mAh/g.
By obtained positive electrode (Li6Co0.995Sn0.005O4)、LiCoO2, conductive agent and binder be according to 3:95.4: The ratio of 0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full battery, surveys Try chemical property.The battery initial charge capacity reaches 211.5mAh/g, and energy density reaches 816Wh/L, and battery passes through 500 After secondary charge and discharge cycles, capacity retention ratio 88.6%.
Embodiment 10
Weigh Li2Ball milling pearl is added by ratio of grinding media to material 4:1 in O 508.0g, LiH 16.0g, using ball mill grinding 30min, Co is added3O4472.0g weighs 6.4g Al2O3, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, ball milling 30min is mixed Close uniform Li2O、LiH、Co3O4And Al2O3Mixture.Resulting material is put into electrothermal furnace 900 DEG C of perseverances under argon atmosphere Warm 12h.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be 12.2 μm of lithium ion battery anodes Material (Li6Co0.98Al0.02O4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 904mAh/g.
By obtained positive electrode (Li6Co0.98Al0.02O4)、LiCoO2, conductive agent and binder be according to 1.2:97.2: The ratio of 0.6:1 is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full battery, surveys Try chemical property.The battery initial charge capacity reaches 198.7mAh/g, and energy density reaches 772Wh/L, and battery passes through 500 After secondary charge and discharge cycles, capacity retention ratio 88.3%.
Embodiment 11
Weigh Li2Ball milling pearl is added by ratio of grinding media to material 4:1 in O 533.4g, LiH 16.8g, using ball mill grinding 30min, Co is added3O4481.6g, while corresponding ball milling pearl is supplemented by ratio of grinding media to material 4:1, ball milling 30min obtains uniformly mixed Li2O、 LiH and Co3O4Mixture.Resulting material is put into electrothermal furnace 900 DEG C of constant temperature 12h under argon atmosphere.After natural cooling It to the first product, is put into ball mill after the first product is crushed, while weighing ZnO, MgO and Al of 17.1g respectively2O3, according to Ball milling pearl is added in the ratio of grinding media to material of 6:1, and the material mixed is put into electrothermal furnace 800 DEG C of perseverances under argon atmosphere by ball milling 20min Warm 4h.It is taken out after being freely cooled to room temperature, grind and is sieved to obtain median particle diameter D50 to be the positive material of 6.6 μm of lithium ion batteries Expect (Li6.05CoO4)。
The charging capacity of electrode prepared by the positive electrode is tested up to 883mAh/g.
By obtained positive electrode (Li6.05CoO4)、LiCoO2, conductive agent and binder be according to 1.2:97.2:0.6:1's Ratio is added a certain amount of solvent and is uniformly mixed, and is coated on aluminium foil, and blending electrode is made and assembles full battery, tests electrochemistry Performance.The battery initial charge capacity reaches 198.5mAh/g, and energy density reaches 761Wh/L, and battery passes through 500 charge and discharge After circulation, capacity retention ratio 89.1%.
Comparative example 1
By LiCoO2, conductive agent, binder a certain amount of solvent is added according to the ratio of 98.4:0.6:1 and is uniformly mixed, apply It is overlying on aluminium foil, anode is made.Negative electrode tab and diaphragm by obtained anode pole piece by cutting, vacuum bakeout and pairing After being wound and being put into plastic-aluminum shell of corresponding size together, inject a certain amount of electrolyte and seal, can be obtained one it is complete Whole lithium ion full battery tests full battery capacity and discharging efficiency using new prestige test equipment BTS79.Full battery is positive for the first time Charging capacity 190.0mAh/g, energy density reach 732Wh/L, and battery is after 500 circulations, capacity retention ratio 89.4%
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention It is interior.

Claims (9)

1. a kind of anode material for lithium ion battery, it is characterised in that: the molecular formula of the positive electrode is Li6+aCo1-xMxO4-b, In, M is doped chemical, 0≤x≤0.1, -0.2≤a≤0.2, -0.2≤b≤0.2；The positive electrode utilizes X-ray diffraction institute The diffraction maximum of generation is Standard Symmetric Multivariate peak shape, the 2 θ angles of diffraction 31.3 ± 0.2 °, 31.8 ± 0.2 °, 32.5 ± 0.2 °, Equal salt free ligands peak at 32.7 ± 0.2 °, 35.0 ± 0.2 °, 37.4 ± 0.2 °, 42.4 ± 0.2 °.
2. anode material for lithium ion battery according to claim 1, it is characterised in that: M be doped chemical Al, Mg, Ti, One of Zr, Si, Zn, Mn, Ni, Sn or a variety of.
3. anode material for lithium ion battery according to claim 1, it is characterised in that: the D50 of the positive electrode is 3 Between~15 μm；The particle diameter distribution width ((D90-D10)/D50) of the positive electrode is between 1.5~2.6；The D90, D50, D10 respectively indicate the partial size that cumulative particle sizes percentile reaches corresponding when 90%, 50%, 10%.
4. anode material for lithium ion battery according to claim 1, it is characterised in that: the positive electrode surface has Substance is coated, the cladding substance is Al2O3、TiO2、SiO2、MgO、ZrO2、AlF3、AlPO4、ZnO、SnO2, in AlOOH one Kind is a variety of, and the covering amount of the cladding substance is 0.1wt%~5wt%.
5. anode material for lithium ion battery according to claim 1, it is characterised in that: the positive electrode for lithium from Specific discharge capacity in sub- battery is higher than 850mAh/g.
6. the preparation method of anode material for lithium ion battery according to claim 1, it is characterised in that: including following step It is rapid:
(1) lithium presoma and cobalt precursor are subjected under low-humidity environment ground and mixed according to a certain percentage, obtain lithium and cobalt Precursor mixture；Alternatively, lithium presoma and cobalt precursor are mixed according to a certain percentage, while being added a certain amount of Doped chemical, three's ground and mixed under low-humidity environment is uniform, obtains the presoma of lithium and cobalt and the mixture of doped chemical；
(2) high temperature sintering is carried out under non-oxidizing atmosphere to mixture obtained by step (1), obtains the first product；
(3) magnetic is crushed, is sieved and removed under low-humidity environment to the first product obtained by step (2), the positive material is made Material；Or the first product obtained by step (2) is carried out the following processing: the first product being crushed under low-humidity environment, will be broken Product after broken is coated, or the first product is carried out to mix cladding under low-humidity environment with pre-coated object, obtains Second product is carried out high temperature sintering by two products under non-oxidizing atmosphere, then be crushed, sieve and remove magnetic, be made it is described just Pole material.
7. the preparation method of anode material for lithium ion battery according to claim 6, it is characterised in that: in step (1),
The lithium presoma and the control of cobalt precursor Li/Co ratio are between 6.0~6.6；
The lithium presoma is lithium hydroxide, in a hydronium(ion) lithia, lithium carbonate, lithium peroxide, lithia, lithium hydride It is one or more；
The cobalt precursor is one of cobaltosic oxide, cobalt protoxide, hydroxide cobalt or a variety of；
The low-humidity environment is at least one in air, nitrogen, argon gas, helium, neon or the Krypton atmosphere of < 10% humidity Kind；
The lapping mode is mechanical lapping, using high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill and sand mill In any one.
8. the preparation method of anode material for lithium ion battery according to claim 6, it is characterised in that: step (2) In:
The temperature of the high temperature sintering is 400~1000 DEG C, and the time is 4~24 hours；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, helium, neon, hydrogen or Krypton.
9. the preparation method of anode material for lithium ion battery according to claim 6, it is characterised in that: in step (3), The crumbling method be mechanical lapping, mechanical lapping using high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill and Any one in sand mill；
The cladding mode uses mechanical fusion or mechanical lapping mode, and the low humidity atmosphere in process of lapping is < 10% humidity At least one of air, nitrogen, argon gas, helium, neon or Krypton atmosphere；
For the high temperature sintering temperature between 400~900 DEG C, the time is 2~12 hours；
Non-oxidizing atmosphere is provided by following at least one gases in the high-temperature sintering process: nitrogen, argon gas, helium, neon Or Krypton.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110718685A (en) * 2019-10-22 2020-01-21 安普瑞斯（南京）有限公司 Silicon-oxygen particles for electrode material and preparation method and application thereof
CN111162258A (en) * 2019-12-31 2020-05-15 安普瑞斯（南京）有限公司 Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material
CN111900394A (en) * 2020-07-03 2020-11-06 清陶（昆山）能源发展有限公司 Coating structure of lithium ion battery anode material and preparation method and application thereof
CN112886002A (en) * 2021-01-14 2021-06-01 宁德新能源科技有限公司 Electrochemical device and electronic apparatus including the same
CN115073157A (en) * 2022-06-16 2022-09-20 安徽锦华氧化锌有限公司 Preparation method of ferrite powder containing zinc oxide, magnesium and zinc
EP4084151A4 (en) * 2021-01-22 2023-09-06 LG Chem, Ltd. Lithium transition metal oxide, positive electrode additive for lithium secondary battery, and lithium secondary battery comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04332480A (en) * 1991-05-07 1992-11-19 Sanyo Electric Co Ltd Nonaqueous secondary battery
US20130171524A1 (en) * 2011-12-30 2013-07-04 Sk Innovation Co., Ltd. Positive active material for rechargeable lithium battery and rechargeable lithium battery including same
CN103682326A (en) * 2013-12-13 2014-03-26 南通瑞翔新材料有限公司 High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof
CN104409700A (en) * 2014-11-20 2015-03-11 深圳市贝特瑞新能源材料股份有限公司 Anode material for nickel-base lithium ion battery and preparation method of anode material
CN107658138A (en) * 2017-09-13 2018-02-02 中南大学 Li6CoO4Prelithiation agent and the preparation method and lithium-ion capacitor of lithium-ion capacitor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04332480A (en) * 1991-05-07 1992-11-19 Sanyo Electric Co Ltd Nonaqueous secondary battery
US20130171524A1 (en) * 2011-12-30 2013-07-04 Sk Innovation Co., Ltd. Positive active material for rechargeable lithium battery and rechargeable lithium battery including same
CN103682326A (en) * 2013-12-13 2014-03-26 南通瑞翔新材料有限公司 High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof
CN104409700A (en) * 2014-11-20 2015-03-11 深圳市贝特瑞新能源材料股份有限公司 Anode material for nickel-base lithium ion battery and preparation method of anode material
CN107658138A (en) * 2017-09-13 2018-02-02 中南大学 Li6CoO4Prelithiation agent and the preparation method and lithium-ion capacitor of lithium-ion capacitor

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110718685A (en) * 2019-10-22 2020-01-21 安普瑞斯（南京）有限公司 Silicon-oxygen particles for electrode material and preparation method and application thereof
CN111162258A (en) * 2019-12-31 2020-05-15 安普瑞斯（南京）有限公司 Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material
CN111900394A (en) * 2020-07-03 2020-11-06 清陶（昆山）能源发展有限公司 Coating structure of lithium ion battery anode material and preparation method and application thereof
CN111900394B (en) * 2020-07-03 2021-03-19 清陶（昆山）能源发展有限公司 Coating structure of lithium ion battery anode material and preparation method and application thereof
CN112886002A (en) * 2021-01-14 2021-06-01 宁德新能源科技有限公司 Electrochemical device and electronic apparatus including the same
CN112886002B (en) * 2021-01-14 2022-06-24 宁德新能源科技有限公司 Electrochemical device and electronic apparatus including the same
EP4084151A4 (en) * 2021-01-22 2023-09-06 LG Chem, Ltd. Lithium transition metal oxide, positive electrode additive for lithium secondary battery, and lithium secondary battery comprising same
EP4084152A4 (en) * 2021-01-22 2023-09-06 Lg Chem, Ltd. Lithium transition metal oxide, cathode additive for lithium secondary battery, and lithium secondary battery comprising same
EP4084150A4 (en) * 2021-01-22 2023-09-06 LG Chem, Ltd. Lithium transition metal oxide, cathode additive for lithium secondary battery, and lithium secondary battery comprising same
CN115073157A (en) * 2022-06-16 2022-09-20 安徽锦华氧化锌有限公司 Preparation method of ferrite powder containing zinc oxide, magnesium and zinc

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Application publication date: 20190910