CN105702936A - Manganese-base carbon-coated nano lithium-rich oxide and preparation method as well as application thereof - Google Patents

Manganese-base carbon-coated nano lithium-rich oxide and preparation method as well as application thereof Download PDF

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CN105702936A
CN105702936A CN201610214412.4A CN201610214412A CN105702936A CN 105702936 A CN105702936 A CN 105702936A CN 201610214412 A CN201610214412 A CN 201610214412A CN 105702936 A CN105702936 A CN 105702936A
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lithium
manganio
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carbon rich
bag carbon
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CN105702936B (en
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李伟善
陈敏
黄启明
廖友好
陈东瑞
钟晓欣
田源源
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South China Normal University
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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
    • 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
    • H01M4/48—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 belongs to the technical field of lithium batteries, and discloses a manganese-base carbon-coated nano lithium-rich oxide and a preparation method as well as an application thereof. The preparation method comprises the following steps: under a condition of stirring, dissolving PVP in DMF, then, adding lithium acetate dihydrate, manganous acetate tetrahydrate, nickel acetate tetrahydrate and cobaltous acetate tetrahydrate according to a molar ratio of 1.26:0.54:0.13:0.13, stirring and dissolving evenly to obtain a metal salt solution; then, heating up the metal salt solution to 60-120 DEG C to carry out constant temperature treatment for 10-24 hours, thereby obtaining a gel-like object; heating up the gel-like object in the air to 400-500 DEG C to carry out constant temperature treatment for 3-8 hours, cooling naturally, then taking out and performing tablet compressing, and sintering for 7-12 hours at the temperature of 800-1000 DEG C to obtain a product. According to the invention, the preparation method is simple, problems, such as hydrolysis and aggregation of transition metal ions, are avoided, and the obtained product has good electrochemical performance when being used as a lithium ion battery positive electrode material.

Description

A kind of manganio bag carbon rich nanometer oxidate for lithium and preparation method thereof and application
Technical field
The invention belongs to lithium battery material technical field, be specifically related to a kind of manganio bag carbon rich nanometer oxidate for lithium and preparation method thereof and application。
Background technology
Along with petering out of whole world fossil energy, environmental pollution increases the weight of day by day, and global energy is abnormal with environmental problem severe, the contradiction of economic growth and resource environment, the sustainable development of human society is brought huge challenge, finds reproducible clean energy resource in the urgent need to us。Lithium ion battery gains great popularity because of advantages such as its energy density are high, have extended cycle life, environmental pollution is little, and positive electrode is as the material of most critical in current lithium ion battery, and its development is also of greatest concern。Manganio stratiform richness oxidate for lithium xLi in recent years2MnO3(1～x) LiMO2(M=Ni, Co, Ni1/2Mn1/2, Ni1/3Mn1/3Co1/3Deng) cause and pay close attention to widely, this is because the embedding lithium capacity that this material is within the scope of 2～4.8V may be up to more than 250mAh/g, it it is the positive electrode that current transition metal series capacity is the highest, and it is main containing resourceful manganese element, cost lower security performance is good, but it is big that this kind of material exists capacitance loss first, high rate performance is poor and the problem of voltage degradation。For solving these problems, people take a lot of method, wherein carbon coated is commonplace and is effectively improved the method for material property, but after method is substantially material preparation, again in material surface carbon coated, this kind of method technique is complex and cladding is difficult to uniform effect, therefore prepares uniform carbon coated stratiform richness lithium material and technique is simply one of primary study direction improving performance of lithium ion battery。
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the primary and foremost purpose of the present invention is in that the preparation method providing a kind of manganio bag carbon rich nanometer oxidate for lithium。
Another object of the present invention is to provide a kind of manganio bag carbon rich nanometer oxidate for lithium prepared by said method。
It is still another object of the present invention to provide the application in anode material for lithium-ion batteries of the above-mentioned manganio bag carbon rich nanometer oxidate for lithium。
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of manganio bag carbon rich nanometer oxidate for lithium, including following preparation process:
Under stirring condition, polyvinylpyrrolidone (PVP) is dissolved in N～N-dimethylformamide (DMF), it is subsequently adding two acetate hydrate lithiums, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts that mol ratio is 1.26:0.54:0.13:0.13, stirring and dissolving is uniform, obtains metal salt solution；Then metal salt solution is warming up to 60～120 DEG C of constant temperature and processes 10～24h, obtain gelling material；Gained jello heats in atmosphere to 400～500 DEG C of constant temperature process 3～8h, takes out tabletting after Temperature fall；Gained tabletting is sintering processes 7～12h at 800～1000 DEG C of temperature, obtains manganio bag carbon rich nanometer oxidate for lithium。
Preferably, described polyvinylpyrrolidone is dissolved in the mass body volume concentrations of N～N-dimethylformamide is 0.1%～2.5%g/mL。
Described polyvinylpyrrolidone (PVP) is a kind of non-ionic macromolecule compound, is most characteristic in N～vinylamide polymer, and be studied the most deeply, fine chemicals kind widely。
A kind of manganio bag carbon rich nanometer oxidate for lithium, is prepared by said method。
The application in anode material for lithium-ion batteries of the above-mentioned manganio bag carbon rich nanometer oxidate for lithium。
Principles of the invention is: utilizes transition metal solubility in the organic solvents such as DMF and has good complexing with DMF, in addition PVP plays good peptizaiton wherein, transition metal salt solution is uniformly dispersed in DMF, compared with in traditional aqueous solution, the phenomenons such as slaine will not be hydrolyzed in organic solvent, reunion。This method design is simple, and single step reaction can be obtained by the rich nanometer lithium material of uniform carbon coated, and this is owing to the peptizaiton of the DMF excellent dissolution effect to slaine and PVP, and the thickness that can keep cladding in follow-up sintering process is homogeneous。The crystal property of synthetic material is good, chemical property is improved a lot by the nano material of uniform carbon coated, this all can provide greatly more reactivity site owing to the specific surface area of nano material, reduces the material with carbon element polarized and be evenly coated and is conducive to the transmission of electronics thus improving the kinetics of reaction。
Preparation method and the obtained product of the present invention have the advantage that and beneficial effect:
(1) preparation method course of reaction simple and fast of the present invention is convenient, it is not necessary to introduce complicated operating process, and in yield height, reaction, free from admixture generates, and economizes on resources。
(2) slaine is dissolved in DMF organic solvent and prepares lithium-rich anode material by the present invention, it is possible to the problem such as hydrolysis reunion preventing transition metal ions。
(3) present invention introduces PVP, the peptizaiton of metal salt solution is differently formed the particle diameter difference to some extent of nano-particle by the PVP of different amounts, and coating thickness is difference to some extent。
(4) the manganio bag carbon rich nanometer oxidate for lithium that preparation method of the present invention obtains has bigger specific surface area, this can increase the contact area of electrode material and electrolyte thus improving the avtive spot of reaction, additionally uniform carbon coating layer improves the electron conduction of material, be conducive to improving kinetics, so that the chemical property of material is improved。
Accompanying drawing explanation
Fig. 1 is the SEM figure of the manganio bag carbon rich nanometer oxidate for lithium material prepared by embodiment 1。
Fig. 2 is the TEM figure of the manganio bag carbon rich nanometer oxidate for lithium material prepared by embodiment 1。
Fig. 3 is the SEM figure of the rich lithium material prepared by comparative example。
The first circle charging and discharging curve comparison diagram of lithium ion battery that Fig. 4 is the manganio bag carbon rich nanometer oxidate for lithium of embodiment 1 preparation and comparative example gained richness lithium material makes。
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this。
Embodiment 1
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 200mL in the hub beaker of 500mL, the rear 0.2gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 800 DEG C of sintering 10h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 2
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 200mL in the hub beaker of 500mL, the rear 1gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 900 DEG C of sintering 10h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 3
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 200mL in the hub beaker of 500mL, the rear 2gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 800 DEG C of sintering 12h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 4
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 300mL in the hub beaker of 500mL, the rear 3gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 500 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 800 DEG C of sintering 12h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 5
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 400mL in the hub beaker of 500mL, the rear 5gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 400 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 900 DEG C of sintering 10h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 6
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 300mL in the hub beaker of 500mL, the rear 2.5gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 100 DEG C, react 10h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 1000 DEG C of sintering 10h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 7
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 100mL in the hub beaker of 500mL, the rear 2gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 100 DEG C, react 8h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 900 DEG C of sintering 12h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Embodiment 8
A kind of preparation method of the manganio bag carbon rich nanometer oxidate for lithium of the present embodiment, concrete preparation process is as follows:
(1) under stirring condition, adding the DMF of 250mL in the hub beaker of 500mL, the rear 1gPVP that adds is sufficiently stirred for 30min, until PVP is dissolved completely in DMF。
(2) under continued mechanical stirs, adding mol ratio to step (1) is that the two acetate hydrate lithiums of 1.26:0.54:0.13:0.13, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts obtain metal salt solution。
(3) under continued mechanical stirs, will the solution warms that obtain in (2) to 80 DEG C, react 12h and obtain gelling material。
(4) gelling material step (3) obtained is sent into Muffle furnace and is warming up to 450 DEG C, constant temperature 5h, takes out tabletting after cooling。
(5) tabletting in (4) is warming up to 1000 DEG C of sintering 8h, manganio bag carbon rich nanometer oxidate for lithium can be obtained and can be used as anode material for lithium-ion batteries。
Comparative example
The manganese sulfate of 2M, nickel sulfate and cobalt sulfate solution join in the sodium carbonate of 2M by metering ratio, regulate pH to 12 with ammonia and heat to 50 DEG C, it is filtrated to get precipitation after continuously stirred 12h, dry 12h will be deposited at 120 DEG C take out and be fully ground post-heating to 900 DEG C of constant temperature 10h with lithium carbonate, take out after natural cooling。Rich lithium material can be obtained。
Physicochemical property is tested:
(1) half-cell assembles: bag carbon rich nanometer lithium material embodiment 1 prepared and the positive electrode of comparative example gained, carries out slurrying with acetylene black and PVDF 8:1:1 in mass ratio and is coated with respectively, being assembled into half-cell with metal lithium sheet for negative pole。
(2) charge-discharge test: bag carbon richness lithium richness lithium embodiment 1 prepared and the positive electrode of comparative example gained, the lithium ion battery of making carries out discharge and recharge under the constant current of 50.0mA/g。
Fig. 1 is the SEM figure of the manganio bag carbon rich nanometer oxidate for lithium of embodiment 1 preparation。As seen from Figure 1, the material obtained by the method for the present invention shows uniform nano-particle, is largely focused on about 200nm。
Fig. 2 is the TEM figure of the manganio bag carbon rich nanometer oxidate for lithium of embodiment 1 preparation。As seen from Figure 2, the material obtained by the method for the present invention shows uniform nano-particle, and appearance is coated with the carbon-coating of one layer of about 5nm uniformly。
Fig. 3 is the SEM figure of rich lithium material prepared by comparative example。As seen from Figure 3, the material obtained by the method for comparative example shows the inhomogenous spheroidal particle of size。
The first circle charging and discharging curve comparison diagram of lithium ion battery that Fig. 4 is the manganio bag carbon rich nanometer oxidate for lithium of embodiment 1 preparation and comparative example gained richness lithium material makes。From fig. 4, it can be seen that the discharge capacity first of embodiment 1 gained manganio bag carbon rich nanometer oxidate for lithium material is 265.0mAh/g, discharging efficiency is 80% first。The discharge capacity first of comparative example gained richness lithium material is 218.0mAh/g, and coulombic efficiency is 68% first。Showing that the manganio bag carbon rich nanometer oxidate for lithium material irreversible capacity loss first prepared by the present invention is low, charge/discharge capacity is high, and its chemical property is more excellent。
Additionally, respectively the manganio bag carbon rich nanometer oxidate for lithium material of embodiment 2～8 gained is carried out slurrying with acetylene black and PVDF 8:1:1 in mass ratio and is coated with, it is assembled into half-cell with metal lithium sheet for negative pole；Then carrying out charge-discharge test under the constant current of 50mA/g, detection obtains:
Embodiment 2 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 252.0mAh/g, coulombic efficiency is 76% first；
Embodiment 3 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 263.0mAh/g, coulombic efficiency is 79% first；
Embodiment 4 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 260.0mAh/g, coulombic efficiency is 80% first；
Embodiment 5 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 250.0mAh/g, coulombic efficiency is 72% first；
Embodiment 6 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 240.0mAh/g, coulombic efficiency is 72% first；
Embodiment 7 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 254.0mAh/g, coulombic efficiency is 78% first；
Embodiment 8 gained manganio bag carbon rich nanometer oxidate for lithium material under anode material for lithium ion battery with high power capacity 50mA/g first discharge capacity be 255.0mAh/g, coulombic efficiency is 75% first。
From Fig. 1～3 and above-mentioned detection data, the manganio bag carbon rich nanometer oxidate for lithium for anode material for lithium ion battery with high power capacity that preparation method of the present invention obtains is the rich nanometer lithium granule of uniform bag carbon, by contrast, adopt the product grain size heterogeneity obtained by traditional co-precipitation method, there is obvious agglomeration, therefore, substantially reduce active substance less with the contact area of electrolyte, the polarization making material is obvious, and stock utilization is relatively low, is unfavorable for the carrying out of electrochemical reaction。
Stating embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention。

Claims (4)

1. the preparation method of a manganio bag carbon rich nanometer oxidate for lithium, it is characterised in that include following preparation process:
Under stirring condition, polyvinylpyrrolidone is dissolved in N～N-dimethylformamide, being subsequently adding two acetate hydrate lithiums, four acetate hydrate manganese, nickel acetate tetrahydrate and four acetate hydrate cobalts that mol ratio is 1.26:0.54:0.13:0.13, stirring and dissolving is uniform, obtains metal salt solution；Then metal salt solution is warming up to 60～120 DEG C of constant temperature and processes 10～24h, obtain gelling material；Gained jello heats in atmosphere to 400～500 DEG C of constant temperature process 3～8h, takes out tabletting after Temperature fall；Gained tabletting is sintering processes 7～12h at 800～1000 DEG C of temperature, obtains manganio bag carbon rich nanometer oxidate for lithium。
2. the preparation method of a kind of manganio bag carbon rich nanometer oxidate for lithium according to claim 1, it is characterised in that: the mass volume ratio of described polyvinylpyrrolidone and N～N-dimethylformamide is 0.1%～2.5%g/mL。
3. a manganio bag carbon rich nanometer oxidate for lithium, it is characterised in that: prepared by the method described in claim 1 or 2。
4. the application in anode material for lithium-ion batteries of the manganio bag carbon rich nanometer oxidate for lithium described in claim 3。
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