CN105680037B - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents

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

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CN105680037B
CN105680037B CN201610167893.8A CN201610167893A CN105680037B CN 105680037 B CN105680037 B CN 105680037B CN 201610167893 A CN201610167893 A CN 201610167893A CN 105680037 B CN105680037 B CN 105680037B
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lithium
ion batteries
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anode material
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CN105680037A (en
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刘韩星
李文姬
余志勇
卢梦云
孙念
马娟
郑振宁
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Wuhan University of Technology WUT
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 anode material for lithium-ion batteries, and it is a kind of novel lamellar multielectron transfer system Li2‑xMo1‑ xCoxO3‑x, 0.05≤x≤0.1.The present invention innovatively synthesizes the material using solid phase method with reference to segmentation control climate method, and the raw material after ball milling mixing is calcined to synthesis presoma first under oxygen atmosphere, then two steps calcining synthesis target product is carried out in reducing atmosphere.The Li of this method synthesis2‑xMo1‑xCoxO3‑xNot only purity is high, granularity is small for powder, layer structure development is more preferable；It is used as battery specific capacity height, the stable cycle performance of anode material for lithium-ion batteries preparation；And the material can avoid oxygen loss, security good in charged state, be adapted to popularization and application.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The invention belongs to new material technology field, and in particular to a kind of Olivine-type Cathode Material in Li-ion Batteries and its preparation side Method.
Background technology
The application of lithium ion battery is just extended from portable type electronic product to electric automobile field.This development trend is to electricity The energy density and power density in pond propose higher requirement.Recently, new multielectron transfer system receives researcher's Pay attention to, it meets development trend of the people to battery request, shows good energy density and height ratio capacity.
In recent years, stratiform multielectron transfer system Li2MoO3Gradually paid close attention to by researchers.Li2MoO3Belong to unordered A-NaFeO2Type structure, due to redox couple Mo in charge and discharge process4+/Mo6+Presence, exchange the system multiple Electronics, thus Li2MoO3Possess higher theoretical specific capacity (339mAh/g), be a kind of potential new type lithium ion battery just Pole material.
The Li of pure phase2MoO3Positive electrode has done a series of researchs also in primary exploratory stage, researcher to its structure, It is but very few to its study on the modification.2014, Gerbrand Ceder seminars of the U.S. synthesized positive electrode at 1050 DEG C Li1.211Mo0.467Cr0.3O2, then it is combined with carbon coating and obtains higher chemical property, the synthesis temperature is higher, because And energy consumption is higher.And other are on pure Li at present2MoO3Study of synthesis method, can use solid phase method to raw material carry out a step also Prepared by original calcining, also can be directly using reduction business Li2MoO4Prepared by the method for powder, these methods can not be prepared completely Very pure Li2MoO3。
The content of the invention
It is an object of the invention to provide a kind of Olivine-type Cathode Material in Li-ion Batteries, and the material is relative to existing polyelectron Transfering system positive electrode possesses higher actual specific capacity, can be effectively improved pure phase Li2MoO3Sill high rate performance difference is asked Topic；And the preparation method being related to is simple, it is adapted to popularization and application.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of anode material for lithium-ion batteries, comprises the following steps：
1) using lithium carbonate, molybdate compound, cobalt compound as raw material, by chemical formula Li2-xMo1-xCoxO3-x(0.05≤x ≤ 0.1) stoichiometric proportion is mixed, and is then disperseed with absolute ethyl alcohol, is then carried out ball milling, is dried to obtain mixed powder Body；
2) the step 1) mixed powder is subjected to atmosphere segmented heat treatment, products therefrom is ground, produces institute The Olivine-type Cathode Material in Li-ion Batteries stated.
In such scheme, molybdenum trioxide, ammonium molybdate etc. can be selected in the molybdate compound.
In such scheme, cobaltosic oxide, basic cobaltous carbonate etc. can be selected in the cobalt compound.
In such scheme, ball-milling technology described in step 1) is 4~6h of ball milling under 800~1000rpm rotating speed.
In such scheme, the atmosphere segmented heat treatment specifically includes following steps：Heat in air atmosphere first To 500~600 DEG C of 6~24h of insulation, persursor material is obtained；After gained persursor material is ground, reducing atmosphere is placed in Two step calcinings of middle progress：650~700 DEG C of 12~24h of insulation (once calcining) are first heated to, after products therefrom takes out and ground It is again heated to 700~800 DEG C of 12~24h of insulation (secondary clacining).
The present invention innovatively synthesizes the anode material for lithium-ion batteries using solid phase method with reference to segmentation control climate method： First by Li2MoO3Co is adulterated to improve the electric conductivity of material；In combination with segmentation control climate method, after ball milling mixing Raw material synthesis presoma is calcined first under oxygen atmosphere, then carry out in reducing atmosphere the calcining of two steps and prepare the material Material, this method can make material crystal structure obtain fully good development, and so as to prepare, purity is higher, granularity is thinner Target product.
In such scheme, H can be selected in the reducing atmosphere2/N2Or H2/Ar2Mixed gas, wherein H2Shared volume ratio For 5~100%.
Preferably, H2Shared volume ratio is 5~10%.
The Olivine-type Cathode Material in Li-ion Batteries prepared according to such scheme, it is a kind of novel lamellar Li2-xMo1- xCoxO3-xSolid-solution material, wherein 0.05≤x≤0.1.
The present invention is by Li2MoO3Positive electrode carries out cobalt doped, and innovatively using simple segmentation control climate Target product is synthesized, its principle is at high temperature (600~1000 DEG C), the MoO in raw material3In hydrogen be it is unstable, It is easy to volatilize, thus the present invention use and carries out low temperature calcination in atmosphere first and form persursor material stably to suppress MoO3 Volatilization；Calcine by steps is then carried out under reducing atmosphere, alleviates persursor material and H2The redox reaction generation of generation Vapor cause the violent phenomenon of abnormal reaction at high temperature.Based on above reason, preparation method of the invention can be prepared It is higher to go out purity, granularity is smaller, the positive electrode of the more excellent stratiform multielectron transfer system of performance, may be implemented in uncombined cladding On the premise of processing, preferable chemical property is obtained with relative lower temperature, there is important practical application and research Reference significance.
Beneficial effects of the present invention are：
1) present invention innovatively combines segmentation control climate method synthesis Li using solid phase method2-xMo1-xCoxO3-x, by right Li2MoO3Material carries out Co doping, and the calcining of the anode material for lithium-ion batteries is realized in reducing atmosphere, effectively improves The specific capacity and high rate performance of products therefrom.
2) present invention combines the high-purity calcining that product can be achieved in the heat treatment of atmosphere segmented, and two steps under reducing atmosphere Calcination process can ensure the growth course of lattice, products therefrom is provided simultaneously with preferable air stability and well-developed layer Shape structure.
3) raw material sources of the present invention are wide, calcination condition is gentle (calcining heat is low)；Products therefrom purity is high, granularity Small, layer structure development is more preferably；Battery specific capacity height, the cycle performance for being used as anode material for lithium-ion batteries preparation are steady It is fixed；And the material can avoid oxygen loss, security good in charged state, be adapted to popularization and application.
Brief description of the drawings
Fig. 1 is the XRD comparison diagrams of comparative example 1 (1) of the present invention and comparative example 2 (2) products therefrom.
Fig. 2 is Li prepared by comparative example 12MoO3- 1, Li prepared by comparative example 22MoO3- 2 and embodiment 1 prepare Li1.9Mo0.9Co0.1O2.9Circulation electric discharge figure under different current densities.
Fig. 3 is the gained Li of embodiment 11.9Mo0.9Co0.1O2.9Scanning electron microscope (SEM) photograph and transmission electron microscope picture.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not For limiting the present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below that Conflict can is not formed between this to be mutually combined.
In following examples, the Li of use2CO3Quality purity be 98%, MoO3Quality purity 99.5%, alkali formula carbon The quality purity of sour cobalt is 50%, and the quality purity of Ammonium Molybdate Tetrahydrate is 99%, Co3O4Quality purity be 99%.
Comparative example 1
Weigh 3.7699g Li2CO3, 7.2332g MoO3Mixed, using absolute ethyl alcohol as dispersant, ball milling 6h, turned Fast 1000r/min, mixed powder is obtained after drying；Gained mixed powder is subjected to segmentation control climate, concretely comprised the following steps：Exist first 600 DEG C of insulation 24h are heated in oxygen atmosphere, obtain Li2MoO3Presoma；Reducing atmosphere is placed in after being ground again (by H2With N2Mixed respectively with the volume fraction of 5% and 95%) two step calcinings of middle progress, wherein a calcination condition is to be warming up to 700 DEG C are calcined 24h, and 700 DEG C of insulation 24h progress secondary clacinings, the final Li for obtaining pure phase are warming up to again after taking out grinding2MoO3 (Li2MoO3-1)。
With 70:20:10 mass ratio weighs Li respectively2MoO3, acetylene black and Kynoar, will grinding it is uniform Li2MoO3(positive electrode) and acetylene black are repeatedly poured slowly into the 1-Methyl-2-Pyrrolidone solvent dissolved with Kynoar, 8-12h is stirred into muddy positive electrode coating, is coated uniformly on coarse stainless steel substrate.By the stainless steel substrate coated (just Pole piece) it is placed in vacuum drying chamber, the positive plate needed for battery assembling is used for after being dried in vacuo 12 hours at 80 DEG C.
CR2025 type button cells, glove box argon gas atmosphere water are assembled into the MBRAUN glove boxes full of high-purity argon gas 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems. Test result shows, under 5mA/g current density, Li2MoO3First discharge specific capacity be 199.6mAh/g, 20 circulations Capability retention afterwards is 68%.
Comparative example 2
Weigh 3.7699g Li2CO3, 7.2332g MoO3Mixed, using absolute ethyl alcohol as dispersant, ball milling 6h, turned Fast 1000r/min, mixed powder is obtained after drying；Gained mixed powder is subjected to segmentation control climate, concretely comprised the following steps：Exist first 600 DEG C of insulation 6h are warming up in air atmosphere, obtain Li2MoO3Presoma；Reducing atmosphere is placed in after being ground again (by H2With N2Mixed respectively with the volume fraction of 5% and 95%) in carry out one-step calcination：700 DEG C of insulation 24h, finally give containing few Measure Li2MoO4Li2MoO3(Li2MoO3-2)。
With 70:20:10 mass ratio weighs Li obtained by this comparative example respectively2MoO3, acetylene black and Kynoar, will grind Grind uniform Li2MoO3(positive electrode) and acetylene black are repeatedly poured slowly into the 1-Methyl-2-Pyrrolidone dissolved with Kynoar In solvent, 8-12h is into muddy positive electrode coating for stirring, is coated uniformly on coarse stainless steel substrate.The stainless steel that will be coated Substrate (positive plate) is placed in vacuum drying chamber, and the positive plate needed for battery assembling is used for after being dried in vacuo 12 hours at 80 DEG C.
Fig. 1 is this comparative example and the gained Li of comparative example 12MoO3XRD comparison diagrams, the results showed that used in reducing atmosphere One-step calcination is not readily available the Li of pure phase2MoO3, and use the Fractional Heat-treatment of the present invention to obtain purer thing phase.
CR2025 type button cells, glove box argon gas atmosphere water are assembled into the MBRAUN glove boxes full of high-purity argon gas 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems, As a result Fig. 2 is seen.The Li that as seen from Figure 2 prepared by comparative example 12MoO3(Li2MoO3- 1) this contrast is substantially better than on electrical property Example (Li2MoO3- 2) sample.Test result shows, under 5mA/g current density, the Li of this comparative example preparation2MoO3Head Secondary specific discharge capacity is 181.1mAh/g, capability retention 60%, and the sample prepared by comparative example 1 is then to have higher put Electric specific capacity and capability retention.
Embodiment 1
Weigh 3.5814g Li2CO3、6.5098g MoO3, 1.0335g basic cobaltous carbonates (CoCO3-3Co(OH)2) mixed Close, using absolute ethyl alcohol as dispersant, with 1000r/min rotating speed ball milling 6h, mixed powder is obtained after drying；By gained mixed powder Body carries out segmentation control climate, concretely comprises the following steps：600 DEG C of insulation 24h are warming up in oxygen atmosphere first, obtain presoma material Material；Reducing atmosphere is placed in after being ground again (by H2And Ar2Mixed respectively with the volume fraction of 5% and 95%) in carry out Two steps are calcined, wherein a calcination condition is warming up to 750 DEG C of insulation 24h again to be warming up to 700 DEG C of insulation 24h after taking out grinding Carry out secondary clacining, the final Li for obtaining pure phase1.9Mo0.9Co0.1O2.9。
With 70:20:10 mass ratio weighs Li respectively1.9Mo0.9Co0.1O2.9, acetylene black and Kynoar, will grinding it is equal Even Li1.9Mo0.9Co0.1O2.9(positive electrode) and acetylene black are repeatedly poured slowly into the 1- methyl -2- pyrroles dissolved with Kynoar In pyrrolidone solvent, 8-12h is into muddy positive electrode coating for stirring, is coated uniformly on coarse stainless steel substrate.By what is coated Stainless steel substrate (positive plate) is placed in vacuum drying chamber, and the positive pole of battery assembling is used for after being dried in vacuo 12 hours at 80 DEG C Piece.
CR2025 type button cells are assembled into the MBRAUN glove boxes full of high-purity argon gas.Glove box argon gas atmosphere water 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems, As a result Fig. 2 is seen, it is shown that the Li obtained by the present embodiment1.9Mo0.9Co0.1O2.9With the gained Li of comparative example 12MoO3At different times Circulation electric discharge figure under rate, under 5mA/g current density, the Li obtained by the present embodiment1.9Mo0.9Co0.1O2.9Discharge ratio first Capacity is 215.6mAh/g, and specific discharge capacity is 175.6mAh/g after circulating 20 times, and capability retention reaches 81.4%, than pure Sample, which is higher by, a lot, illustrates that Co introducing not only makes material capacity increase, while also reduces the attenuation rate of material.Meanwhile Under different multiplying (5,10,20mA/g), the specific discharge capacity of the present embodiment resulting materials substantially has than the resulting materials of comparative example 1 Improved, especially under higher multiplying power, illustrate that Co introducing also improves the high rate performance of material.Fig. 3 is the present embodiment institute Obtaining (a) scanning electron microscope (SEM) photograph and (b) transmission electron microscope picture of product, it can be seen that obvious sheet, layer structure distribution is presented in material, And lattice fringe is clearly obvious on transmission electron microscope picture, is stacked and formed by some thin slices.
Embodiment 2
Weigh 3.6757Li2CO3、6.8715g MoO3, 0.5168g basic cobaltous carbonates (CoCO3-3Co(OH)2) mixed Close, using absolute ethyl alcohol as dispersant, rotating speed obtains mixed powder with 1000r/min rotating speed ball milling 4h after drying；Gained is mixed Close powder and carry out segmentation control climate, concretely comprise the following steps：600 DEG C of insulation 12h are warming up in oxygen atmosphere first, obtain forerunner Body material；Reducing atmosphere is placed in after being ground again (by H2And N2Mixed respectively with the volume fraction of 5% and 95%) in enter The step of row two is calcined, wherein a calcination condition is warming up to 750 DEG C of insulations again to be warming up to 650 DEG C of insulation 24h after taking out grinding 24h carries out secondary clacining., the final Li for obtaining pure phase1.95Mo0.95Co0.05O2.95。
With 70:20:10 mass ratio weighs Li respectively1.95Mo0.95Co0.05O2.95, acetylene black and Kynoar.It will grind Grind uniform Li1.95Mo0.95Co0.05O2.95(positive electrode) and acetylene black are repeatedly poured slowly into the 1- first dissolved with Kynoar In base -2-Pyrrolidone solvent, 8-12h is into muddy positive electrode coating for stirring, is coated uniformly on coarse stainless steel substrate.Will The positive plate coated is placed in vacuum drying chamber, and battery is used for after being dried in vacuo 12 hours at 80 DEG C and is assembled.
CR2025 type button cells are assembled into the MBRAUN glove boxes full of high-purity argon gas.Glove box argon gas atmosphere water 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems. Test result shows, under 5mA/g current density, its first discharge specific capacity is 213.4mAh/g, capacity after 20 circulations Conservation rate is 70.1%.
Embodiment 3
Weigh 3.5814g Li2CO3, 8.0251g Ammonium Molybdate Tetrahydrates, 0.4054g Co3O4Mixed, with anhydrous second Alcohol, with 1000r/min rotating speed ball milling 4h, obtains mixed powder as dispersant after drying；Gained mixed powder is segmented Control climate, concretely comprise the following steps：500 DEG C of insulation 24h are heated in oxygen atmosphere first, obtain persursor material；Ground Reducing atmosphere is placed in after mill again (by H2And N2Mixed respectively with the volume fraction of 10% and 90%) two step calcinings of middle progress, A wherein calcination condition takes out and 800 DEG C of insulation 24h secondary clacinings is again heated to after grinding to be heated to 700 DEG C of insulation 24h, The final Li for obtaining pure phase1.9Mo0.9Co0.1O2.9。
With 70:20:10 mass ratio weighs Li respectively1.9Mo0.9Co0.1O2.9, acetylene black and Kynoar.It will grind equal Even Li1.9Mo0.9Co0.1O2.9(positive electrode) and acetylene black are repeatedly poured slowly into the 1- methyl -2- pyrroles dissolved with Kynoar In pyrrolidone solvent, 8-12h is into muddy positive electrode coating for stirring, is coated uniformly on coarse stainless steel substrate.By what is coated Stainless steel substrate (positive plate) is placed in vacuum drying chamber, and the positive pole of battery assembling is used for after being dried in vacuo 12 hours at 80 DEG C Piece.
CR2025 type button cells are assembled into the MBRAUN glove boxes full of high-purity argon gas.Glove box argon gas atmosphere water 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems, Test result shows, under 5mA/g current density, its first discharge specific capacity is 219.7mAh/g, capacity after 20 circulations Conservation rate is 80%.
Embodiment 4
Weigh 3.6757g Li2CO3, 8.4709g Ammonium Molybdate Tetrahydrates, 0.5168g basic cobaltous carbonates (CoCO3-3Co (OH)2) mixed, using absolute ethyl alcohol as dispersant, with 800r/min rotating speed ball milling 6h, mixed powder is obtained after drying, Gained mixed powder is subjected to segmentation control climate, concretely comprised the following steps：500 DEG C of insulation 24h are heated in oxygen atmosphere first, Obtain persursor material；H is placed in after being ground again2Reducing atmosphere in carry out two step calcinings, wherein a calcination condition is 700 DEG C of insulation 24h are heated to, 750 DEG C of insulation 12h progress secondary clacinings is again heated to after taking out grinding, finally gives pure phase Li1.95Mo0.95Co0.05O2.95。
With 70:20:10 mass ratio weighs Li respectively1.95Mo0.95Co0.05O2.95, acetylene black and Kynoar, will grind Grind uniform Li1.95Mo0.95Co0.05O2.95(positive electrode) and acetylene black are repeatedly poured slowly into the 1- first dissolved with Kynoar In base -2-Pyrrolidone solvent, 8-12h is into muddy positive electrode coating for stirring, is coated uniformly on coarse stainless steel substrate.Will The stainless steel substrate (positive plate) coated is placed in vacuum drying chamber, and battery assembling is used for after being dried in vacuo 12 hours at 80 DEG C Positive plate.
CR2025 type button cells are assembled into the MBRAUN glove boxes full of high-purity argon gas.Glove box argon gas atmosphere water 0.1ppm is maintained at oxygen.Wherein negative pole uses metal lithium sheet, electrolyte EC:DMC(1:1, v:V), barrier film is Celgard.The charge-discharge performance (1.5~4.5V of voltage range) of battery is characterized using Land CT2001A battery test systems. Test result shows, under 5mA/g current density, first discharge specific capacity 215.1mAh/g, and the capacity after 20 circulations Conservation rate is 71.3%.
Each raw material proportioning cited by the present invention can realize the present invention, and the bound value of each raw material, interval value The present invention can be realized, the bound value of technological parameter of the invention and section can realize the present invention, herein not one by one Citing.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included Within protection scope of the present invention.

Claims (6)

1. a kind of preparation method of anode material for lithium-ion batteries, it is characterised in that comprise the following steps：
1）Using lithium carbonate, molybdate compound, cobalt compound as raw material, by chemical formula Li2-xMo1-xCoxO3-x, 0.05≤x≤0.1 Stoichiometric proportion mixed, then disperseed with absolute ethyl alcohol, then carry out ball milling, dry to obtain mixed powder；
2）By step 1）The mixed powder carries out atmosphere segmented heat treatment, and products therefrom is ground, and produces described Anode material for lithium-ion batteries；
The atmosphere segmented heat treatment step is：500 ~ 600 DEG C of 6 ~ 24h of insulation are heated in air atmosphere first, before obtaining Drive body material；It is placed in after grinding in reducing atmosphere and is first heated to 650 ~ 700 DEG C of 12 ~ 24h of insulation, products therefrom takes out and ground 700 ~ 800 DEG C of 12 ~ 24h of insulation are again heated to after mill, carry out two step calcinings.
2. preparation method according to claim 1, it is characterised in that the molybdate compound is molybdenum trioxide or molybdic acid Ammonium.
3. preparation method according to claim 1, it is characterised in that the cobalt compound is cobaltosic oxide or alkali Formula cobalt carbonate.
4. preparation method according to claim 1, it is characterised in that step 1）Described in ball-milling technology be 800 ~ 1000 4 ~ 6h of ball milling under rpm rotating speed.
5. preparation method according to claim 1, it is characterised in that the reducing atmosphere is H2And N2Or H2And Ar2It is mixed Close gas, wherein H2Shared volume fraction is 5 ~ 100%.
6. anode material for lithium-ion batteries made from any one of claim 1 ~ 5 preparation method, it is characterised in that it is layer Shape Li2-xMo1-xCoxO3-x, 0.05≤x≤0.1.
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