CN104868116B - Anode material for lithium-ion batteries LiMn2 3xM (II) xAlxSixO4 and preparation method thereof - Google Patents

Anode material for lithium-ion batteries LiMn2 3xM (II) xAlxSixO4 and preparation method thereof Download PDF

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CN104868116B
CN104868116B CN201510229269.1A CN201510229269A CN104868116B CN 104868116 B CN104868116 B CN 104868116B CN 201510229269 A CN201510229269 A CN 201510229269A CN 104868116 B CN104868116 B CN 104868116B
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lithium
raw material
ion batteries
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anode material
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CN104868116A (en
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刘兴泉
赵红远
熊伟强
陈炳
张峥
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University of Electronic Science and Technology of China
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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
    • H01M4/58—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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 anode material for lithium-ion batteries preparation field, there is provided a kind of anode material for lithium-ion batteries and preparation method thereof, the positive electrode have following chemical formula LiMn2‑3xM(II)xAlxSixO4, wherein M (II)=Mg, Ni, Co, Zn, Cu, 0≤x≤0.15.Its preparation method be by a certain amount of citric acid and lithium source dissolution of raw material in deionized water, it is slowly added into manganese source raw material, doped chemical raw material in proportion in resulting solution, rufous wet gel is obtained using sol gel process, pre-burning 4h~6h in 400 DEG C~450 DEG C at a temperature of is put in Muffle furnace after to be dried, pre-burning 15h~24h at a temperature of 700 DEG C~850 DEG C is put in Muffle furnace again after finally taking out grinding, that is, obtains target product.Anode material for lithium-ion batteries prepared by this method is without dephasign; crystalline quality is high; particle size is evenly distributed; with higher specific discharge capacity and excellent cyclical stability; high rate charge-discharge demand is disclosure satisfy that, and operating procedure is simple, and raw material sources are extensive; manufacturing cost is low, it is easy to accomplish scale industrial production.

Description

Anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4And preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, is related to anode material for lithium-ion batteries and preparation method thereof, specially lithium Ion battery positive electrode LiMn2-3xM(II)xAlxSixO4And preparation method thereof, wherein M (II)=Mg, Ni, Co, Zn, Cu etc. two Valence metal ion.
Background technology
With the worsening of global environment and weather, energy-saving and emission-reduction are extremely urgent, in international community also increasingly Focus on the exploitation and application of new energy and renewable and clean energy resource.Lithium ion battery is as excellent performance and the electricity of environmental protection Pond, have energy density height, quickly-chargeable, self discharge it is small, can long-time storage, the superior, memory-less effect of cycle performance etc. Advantage.Lithium ion battery is had been widely used on various portable electric appts, also by as the first choice of following electric automobile Power supply.
Batch application mainly has cobalt acid lithium (LiCoO in the positive electrode of lithium ion battery at present2), lithium nickelate (LiNiO2), LiFePO4 (LiFePO4), nickle cobalt lithium manganate (LNCM) and lithium manganate having spinel structure (LiMn2O4).Wherein, cobalt Sour lithium is to realize commercial applications earliest, and technology of preparing has developed into ripe so far, and is widely used to compact low power Portable type electronic product on, but the toxicity of cobalt is larger, scarcity of resources, causes the manufacturing cost of lithium ion battery high；Lithium nickelate The security of battery is worst, overcharge easily it is on fire, easily decomposed under high temperature, make its thermal stability poor, commercialization process by It is certain to hinder；Lithium iron phosphate positive material is environment-protecting and non-poisonous, and rich in mineral resources, low raw-material cost, temperature tolerance is splendid, follows Ring stability is superior, but its electric conductivity is poor, and density is small, and volume is big, and energy density is low and cryogenic property is not good enough, makes its application It is restricted with development.
Spinel structure LiMn2O4 LiMn2O4Positive electrode is the semi-conducting material for having three-dimensional lithium ion mobility passage, Three-dimensional tunnel structure is advantageous to the insertion and abjection of lithium ion, and deintercalation current potential is high, and power density is big, the aboundresources of manganese, price It is cheap, it is environmentally safe, therefore lithium manganate having spinel structure positive electrode is most possibly to replace cobalt acid lithium to turn into a new generation to produce The anode material for lithium-ion batteries of industry.Application prospect especially in terms of electrokinetic cell and energy-storage battery is preferable.However, point is brilliant The theoretical specific capacity of stone-type LiMn2O4 is not high (only 148mAh/g), it is difficult to pure phase product is made, has occurred in cyclic process Jahn-Teller effects, influence the service life of lithium ion battery.In high temperature environments, due to the dissolving of manganese, spinel-type The cycle performance of LiMn2O4 is more unstable.So far, the preparation of lithium manganate having spinel structure is generally completed using solid phase method, the party The raw material that are mainly characterized by reacting of method are carried out directly in a manner of taking solid-phase sintering after being sufficiently mixed in the form of solid phase uniformly Reaction forms powder crystal, and lithium source and manganese source are typically respectively LiOHH2O、Li2CO3、LiNO3、MnO2、Mn(NO3)2、MnCO3、 Mn(CH3COO)2·4H2O, hydrated manganese dioxide, Mn2O3Deng, grinding or ball milling after carry out high temperature sintering.This method technique Simply, it is adapted to commercially produce, but the synthesis in solid state time is longer, and power consumption is high, particle size skewness, it is difficult to prepares chemistry The target product of ratio is measured, chemical property is poor.Therefore, the electrochemical stability of lithium manganate having spinel structure positive electrode is improved Can, the composition and preparation technology for optimizing manganate cathode material for lithium turn into current important process.
The content of the invention
It is an object of the invention to for anode material for lithium-ion batteries lithium manganate having spinel structure (LiMn2O4) electrochemistry follows A kind of the shortcomings that ring poor performance, there is provided bulk phase-doped modified spinel-type lithium-ion cell positive material LiMn2-3xM(II)xAlxSixO4And preparation method thereof, the bivalent metal ion such as wherein M (II)=Mg, Ni, Co, Zn, Cu.The lithium ion cell positive Material LiMn2-3xM(II)xAlxSixO4With higher specific discharge capacity and excellent stable circulation performance, big times disclosure satisfy that Rate charge-discharge power demand, its preparation method overcome solid-phase synthesis preparation time length, unmanageable stoichiometric proportion, particle size The shortcomings of skewness and chemical property difference, product purity height, chemical homogeneous height, crystalline quality height, the product of preparation Particle is tiny and be evenly distributed, excellent electrochemical performance and manufacturing cost it is low.
The technical scheme is that：Anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4, it is characterised in that The biomolecule expressions of the anode material for lithium-ion batteries are LiMn2-3xM(II)xAlxSixO4, wherein M (II)=Mg, Ni, Co, The bivalent metal ions such as Zn, Cu, 0≤x≤0.15.
Anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4Preparation method, it is characterised in that including following step Suddenly：
Step 1. is by lithium source raw material and complexing agent citric acid in molar ratio 1:1 is dissolved in appropriate amount of deionized water, and is placed on Stirred in 50 DEG C of water-baths, it is completely dissolved to obtain solution A；
Step 2. is by manganese source raw material, doping divalent metal element raw material and aluminium source raw material Mn in molar ratio:M(II):Al =(2-3x):x:X is dissolved in appropriate amount of deionized water, obtains solution B；
Step 3. by with doping divalent metal element raw material equimolar than silicon source dissolution of raw material in appropriate absolute ethyl alcohol or In person's deionized water, the alcoholic solution or suspension C of silicon source raw material are obtained；
Step 4. slowly instills step 2,3 resulting solution B, alcoholic solution or suspension C obtained by step 1 dropwise simultaneously In solution A, and it is stirred continuously to obtain mixed solution.
Step 5. is 6~8 to step 4 gained mixed solution and dripping ammoniacal liquor, regulation pH value, is warming up to after stirring 30min 70 DEG C, it is stirred continuously to moisture evaporation, forms rufous gel；
Step 5 gained rufous gel is put in air dry oven by step 6., and 24h is dried at 110 DEG C~120 DEG C and is obtained To xerogel；
Step 6 gained xerogel is put in Muffle furnace by step 7., and low temperature presintering 4h~6h is obtained at 400 DEG C~450 DEG C To intermediate product；
Step 8. grinds step 7 gained intermediate product Spinel-type lithium-ion cell positive material LiMn can be made2-3xM(II)xAlxSixO4。
In step 1, the lithium source raw material is lithium acetate, lithium carbonate, lithium nitrate, lithium citrate, lithium oxalate and hydroxide At least one of lithium.
In step 2, the manganese source raw material be manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate and manganese hydroxide and At least one of oxide (chemical manganese bioxide and electrolytic manganese dioxide).
In step 2, the doping divalent metal element raw material is acetate, carbonate, the nitric acid of corresponding doped chemical Salt, oxalates and at least one of hydroxide and oxide.
In step 2, source of aluminium raw material is at least one of aluminum nitrate, aluminium chloride, aluminum sulfate.
In step 3, the silicon source raw material is at least one in tetraethyl orthosilicate, silica, silicic acid and silicate Kind；If it is silicon source raw material to select tetraethyl orthosilicate, using Organic Alcohol as solvent, the Organic Alcohol with obtained tetraethyl orthosilicate is molten Liquid；If at least one of silica, silicic acid and silicate is selected to be used as silicon source raw material, using deionized water as molten Agent, with obtained corresponding suspension.
In step 4, the lithium source raw material, manganese source raw material, doping divalent metal element raw material, aluminium source raw material and silicon source The mol ratio of raw material is Li:Mn:M(II):Al:Si=(1~1.1):(2-3x):x:x:x.
The present invention adulterates quadrivalent element, triad and diad by equimolar simultaneously and substituted in positive electrode Manganese element obtains anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4.Aluminium is III Main Group Metal Elements, its valence state is+ Trivalent, trivalent aluminium ion substitute the manganese element in positive electrode to reduce Mn3+Amount, reduce Jahn-Teller effects to positive pole The influence of material structure, be advantageous to improve the structural stability and electrochemistry cycle performance of positive electrode.Silicon is the non-gold of IV main groups Belong to element, its valence state is+4 valencys, and the introducing of tetravalence silicon ion has following benefit：(1) addition of silicon ion can optimize parent material The electric conductivity of material, improve its high rate during charging-discharging；(2) because the silicon ion of doping is in+4 valencys, higher than manganese in fertile material The valency of average valence+3.5, silicon ion doping After-market fertile material is presented n-type semiconductor property, can not only suppress manganese under high temperature The dissolving of ion, the electric conductivity of positive electrode and the redox property of manganese ion can also be increased, make the electrification of positive electrode Performance is learned preferably to be played；(3) due to+4 valency silicon ions ,+trivalent aluminium ion and+divalent doped metal ion are equimolars Adulterate, Mn in fertile material4+/Mn3+(mol ratio) is more than 1, can effectively suppress Jahn-Teller effects.In addition, silicon is first Element has very strong structure effect and temperature effect, and doping addition tetravalence element silicon advantageously reduces sintering temperature, improves positive pole The structural stability of material, increase the cycle life of positive electrode.
The present invention prepares anode material for lithium-ion batteries LiMn using sol-gal process2-3xM(II)xAlxSixO4, wherein M (II) bivalent metal ions such as=Mg, Ni, Co, Zn, Cu.Compared with solid phase method, the chemical reaction of sol-gal process is easily carried out, And only need relatively low synthesis temperature, it is considered that the diffusion of components in sol-gel system is in nanometer range, and solid phase The diffusion of each component is in micrometer range in course of reaction.
In summary, the invention has the advantages that：
1st, the present invention uses sol-gal process technique, metal ion is fixed by organic complexing agent, reaction raw materials mix Close uniform, the shortcomings that overcoming conventional solid synthetic method, the product crystalline quality of preparation is excellent, chemical uniformity is good, particle is thin It is small, purity is high.
2nd, spinel-type lithium-ion cell positive material LiMn prepared by the present invention2-3xM(II)xAlxSixO4In ,+divalent is mixed Miscellaneous metallic element ,+trivalent aluminium element and+4 valency element silicons are added in equimolar ratio, can be fully by means of each doping member The advantage of element, improve the combination property of positive electrode.
3rd, spinel-type lithium-ion cell positive material LiMn prepared by the present invention2-3xM(II)xAlxSixO4With higher Specific discharge capacity and excellent stable circulation performance, suitable for high rate charge-discharge demand；Under room temperature environment, when constant current fills When discharge-rate is 0.5C, the first discharge specific capacity of the spinel-type lithium-ion cell positive material can reach 123.4mAh/ G, 120.5 are still can reach after circulating 50 times, capability retention is up to 97.6%.
4th, reaction raw material used are all general chemical products in technique of the invention, and abundance is cheap, manufacture Cost is low.
5th, device therefor is simple in technique of the invention, is produced in preparation process without poisonous and harmful substance, both meets green Environmentally friendly concept, is easily achieved scale industrial production again.
Brief description of the drawings
Fig. 1 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4Process chart.
Fig. 2 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4XRD.
Fig. 3 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4SEM figure.
Fig. 4 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4Head under 0.5C multiplying powers Secondary charging and discharging curve figure.
Fig. 5 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4Following under 0.5C multiplying powers Ring performance chart.
Fig. 6 is that the present invention prepares anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4Storehouse under 0.5C multiplying powers Logical sequence efficiency curve diagram.
Embodiment
With reference to specific embodiment, the present invention is described in further detail with accompanying drawing.
Embodiment 1
By 0.0525mol (2.2029g) lithium hydroxides and 0.0525mol (11.0324g) citric acid be dissolved in it is appropriate go from In sub- water, and it is placed in 50 DEG C of water-baths and stirs, makes it be completely dissolved to obtain solution A；By 0.0925mol (22.6708g) acetic acid Manganese, 0.0025 mol (0.6410g) magnesium nitrates and 0.0025mol (0.9378g) aluminum nitrate are dissolved in deionized water and prepared Obtain mixed salt solution B；0.0025mol (0.5469g) tetraethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol and obtains the second of tetraethyl orthosilicate Alcoholic solution C.
The ethanol solution C of mixed salt solution B and tetraethyl orthosilicate is slowly added dropwise in solution A simultaneously, and constantly stirred Mix, be 8 with ammoniacal liquor regulation pH value, 70 DEG C are warming up to after stirring 30min, and continue stirring untill rufous gel is produced；So Afterwards by obtained rufous gel in air dry oven 110 DEG C of dry 24h, then be put in 450 DEG C of low temperature presinterings 4 in Muffle furnace h；Finally obtained intermediate product is taken out and ground, the pre-burning 18h at a temperature of 750 DEG C is put in Muffle furnace and can be prepared by spinelle Type anode material for lithium-ion batteries LiMn1.85Mg0.05Al0.05Si0.05O4。
To the anode material for lithium-ion batteries LiMn of preparation1.85Mg0.05Al0.05Si0.05O4Constant current charge-discharge test is carried out, From test result it can be seen that the positive electrode has higher specific discharge capacity and excellent stable circulation performance, suitable for big Rate charge-discharge demand；Under room temperature environment, when constant current charge-discharge multiplying power is 0.5C, the spinel-type lithium-ion battery is just The first discharge specific capacity of pole material can reach 123.4mAh/g, still can reach 120.5 after circulating 50 times, capability retention Up to 97.6%.
Embodiment two：
By 0.0263mol (1.1015g) lithium hydroxides and 0.0263mol (5.5162g) citric acid be dissolved in it is appropriate go from In sub- water, and it is placed in 50 DEG C of water-baths and stirs, makes it be completely dissolved to obtain solution A；By 0.0463mol (11.3354g) acetic acid Manganese, 0.0013 mol (0.2744g) zinc acetates and 0.0013mol (0.4689g) aluminum nitrate are dissolved in deionized water and prepared Obtain mixed salt solution B；0.0013mol (0.2735g) tetraethyl orthosilicate is dissolved in appropriate absolute ethyl alcohol and obtains the second of tetraethyl orthosilicate Alcoholic solution C.
The ethanol solution C of mixed salt solution B and tetraethyl orthosilicate is slowly added dropwise in solution A simultaneously, and constantly stirred Mix, be 8 with ammoniacal liquor regulation pH value, 70 DEG C are warming up to after stirring 30min, and continue stirring untill rufous gel is produced；So Afterwards by obtained rufous gel in air dry oven 110 DEG C of dry 24h, then be put in 450 DEG C of low temperature presinterings 4 in Muffle furnace h；Finally obtained intermediate product is taken out and ground, the pre-burning 18h at a temperature of 750 DEG C is put in Muffle furnace and can be prepared by spinelle Type anode material for lithium-ion batteries LiMn1.85Zn0.05Al0.05Si0.05O4, its effect and performance are substantially the same manner as Example 1.

Claims (10)

1. anode material for lithium-ion batteries LiMn2-3xM(II)xAlxSixO4, it is characterised in that the anode material for lithium-ion batteries Biomolecule expressions be LiMn2-3xM(II)xAlxSixO4, wherein M (II)=Mg, Ni, Zn, Cu, 0<x≤0.15.
2. the anode material for lithium-ion batteries LiMn as described in claim 12-3xM(II)xAlxSixO4Preparation method, its feature exists In comprising the following steps：
Step 1. is by lithium source raw material and complexing agent citric acid in molar ratio 1:1 is dissolved in appropriate amount of deionized water, and is placed on 50 DEG C Stirred in water-bath, it is completely dissolved to obtain solution A；
Step 2. is by manganese source raw material, doping divalent metal element raw material and aluminium source raw material Mn in molar ratio:M(II):Al=(2- 3x):x:X is dissolved in appropriate amount of deionized water, obtains solution B；
Step 3. by with doping divalent metal element raw material equimolar than silicon source dissolution of raw material in appropriate absolute ethyl alcohol or go In ionized water, the alcoholic solution or suspension C of silicon source raw material are obtained；
Step 2,3 resulting solution B, alcoholic solution or suspension C are slowly instilled step 1 resulting solution by step 4. dropwise simultaneously In A, and it is stirred continuously to obtain mixed solution；
Step 5. is 6~8 to step 4 gained mixed solution and dripping ammoniacal liquor, regulation pH value, and 70 DEG C are warming up to after stirring 30min, It is stirred continuously to moisture evaporation, forms rufous gel；
Step 5 gained rufous gel is put in air dry oven by step 6., and 24h is dried at 110 DEG C~120 DEG C and is done Gel；
Step 6 gained xerogel is put in Muffle furnace by step 7., during low temperature presintering 4h~6h is obtained at 400 DEG C~450 DEG C Between product；
Step 8. can uniformly make the grinding of step 7 gained intermediate product after high-temperature roasting 15h~24h at 700 DEG C~850 DEG C Obtain spinel-type lithium-ion cell positive material LiMn2-3xM(II)xAlxSixO4。
3. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In, in step 4, the lithium source raw material, manganese source raw material, doping divalent metal element raw material, aluminium source raw material and silicon source raw material Mol ratio is Li:Mn:M(II):Al:Si=(1~1.1):(2-3x):x:x:x.
4. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In, in step 1, the lithium source raw material be lithium acetate, lithium carbonate, lithium nitrate, lithium citrate, lithium oxalate and lithium hydroxide in extremely Few one kind.
5. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In in step 2, the manganese source raw material is the hydroxide and oxide of manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate and manganese At least one of (chemical manganese bioxide and electrolytic manganese dioxide).
6. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In in step 2, the doping divalent metal element raw material is acetate, carbonate, nitrate, the oxalic acid of corresponding doped chemical Salt and at least one of hydroxide and oxide.
7. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In in step 2, source of aluminium raw material is at least one of aluminum nitrate, aluminium chloride, aluminum sulfate.
8. the anode material for lithium-ion batteries LiMn as described in claim 22-3xM(II)xAlxSixO4Preparation method, its feature exists In in step 3, the silicon source raw material is at least one of tetraethyl orthosilicate, silica, silicic acid and silicate.
9. the anode material for lithium-ion batteries LiMn as described in claim 82-3xM(II)xAlxSixO4Preparation method, its feature exists In, the silicon source raw material is tetraethyl orthosilicate, using Organic Alcohol as solvent, organic alcoholic solution with obtained tetraethyl orthosilicate.
10. the anode material for lithium-ion batteries LiMn as described in claim 82-3xM(II)xAlxSixO4Preparation method, its feature It is, the silicon source raw material is at least one of silica, silicic acid and silicate, using deionized water as solvent, With obtained corresponding suspension.
CN201510229269.1A 2015-05-07 2015-05-07 Anode material for lithium-ion batteries LiMn2 3xM (II) xAlxSixO4 and preparation method thereof Expired - Fee Related CN104868116B (en)

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