CN104868116A - Lithium ion cell anode material LiMn2-3*M(II)*Al*Si*O4 and preparation method thereof - Google Patents

Lithium ion cell anode material LiMn2-3*M(II)*Al*Si*O4 and preparation method thereof Download PDF

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CN104868116A
CN104868116A CN201510229269.1A CN201510229269A CN104868116A CN 104868116 A CN104868116 A CN 104868116A CN 201510229269 A CN201510229269 A CN 201510229269A CN 104868116 A CN104868116 A CN 104868116A
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lithium
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CN104868116B (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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the preparation field of the lithium ion cell anode material, and provides a lithium ion cell anode material and a preparation method thereof. The anode material has the following chemical formula: LiMn2-3*M(II)*Al*Si*O4, wherein M(II) is equal to M9, Ni, Co, Zn, and Cu, x is greater than or equal to 0, and less than or equal to 0.15. The preparation method is as follows: dissolving a certain amount of citric acid and lithium source raw material in the deionized water, slowly adding the lithium source raw material and doping element raw material to the obtained solution in proportion, obtaining the reddish brown wet gel by the sol gel technology, pre-burning for 4-6 h in a muffle furnace under 400-450 DEG C of the temperature after drying, finally pre-burning for 15-24 h in the muffle furnace under 700-850 DEG C of the temperature again after taking out and grinding, and obtaining the target product directly. The lithium ion cell anode material prepared by the method has no impurity phase, high crystal quality, symmetrical product size distribution, higher discharge specific capacity, excellent cycling stability, simple operation technology, extensive raw material source, and low manufacturing cost, is capable of satisfying the large multiplying power discharging-charging requirements, and easy to achieve the large-scale industrial production.

Description

Anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, relate to anode material for lithium-ion batteries and preparation method thereof, be specially anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4and preparation method thereof, the wherein bivalent metal ion such as M (II)=Mg, Ni, Co, Zn, Cu.
Background technology
Along with going from bad to worse of global environment and weather, energy-saving and emission-reduction are extremely urgent, international community also more and more pay close attention to the development & application of new forms of energy and renewable and clean energy resource.Lithium ion battery as excellent performance and the battery of environmental protection, has that energy density is high, quickly-chargeable, self discharge is little, can the advantage such as superior, the memory-less effect of long-time storage, cycle performance.Lithium ion battery has been widely used on various portable electric appts, also will become the first-selected power supply of following electric automobile.
The positive electrode being applied to lithium ion battery at present in batches mainly contains cobalt acid lithium (LiCoO 2), lithium nickelate (LiNiO 2), LiFePO4 (LiFePO 4), nickle cobalt lithium manganate (LNCM) and lithium manganate having spinel structure (LiMn 2o 4).Wherein, cobalt acid lithium realizes commercial applications the earliest, and technology of preparing is full-fledged so far, and is widely used on the portable type electronic product of compact low power, but the toxicity of cobalt is comparatively large, and scarcity of resources, causes the manufacturing cost of lithium ion battery high; The fail safe of lithium nickelate battery is the poorest, overcharges easily on fire, easily decomposes under high temperature, and make its thermal stability poor, commercialization process is subject to certain obstruction; Lithium iron phosphate positive material environment-protecting asepsis, rich in mineral resources, low raw-material cost, temperature tolerance is splendid, stable circulation performance is superior, but its conductivity is poor, and density is little, volume is large, and energy density is low and cryogenic property is not good enough, and its application and development is all restricted.
Spinel structure LiMn2O4 LiMn 2o 4positive electrode is the semi-conducting material with three-dimensional lithium ion mobility passage, three-dimensional tunnel structure is conducive to the embedding of lithium ion and deviates from, deintercalation current potential is high, power density is large, the aboundresources of manganese, cheap, environmentally safe, therefore lithium manganate having spinel structure positive electrode is the anode material for lithium-ion batteries most possibly replacing cobalt acid lithium to become industrialization of new generation.Especially the application prospect in electrokinetic cell and energy-storage battery is better.But the theoretical specific capacity of lithium manganate having spinel structure is not high (only 148mAh/g), is difficult to obtained pure phase product, in cyclic process, Jahn-Teller effect has occurred, affect the useful life of lithium ion battery.In high temperature environments, due to the dissolving of manganese, the cycle performance of lithium manganate having spinel structure is more unstable.Up to now, the preparation of lithium manganate having spinel structure generally adopts solid phase method to complete, the principal character of the method takes the mode of solid-phase sintering to carry out directly reaction after reaction raw material fully mix with the form of solid phase to form powder crystal, and lithium source and manganese source are generally respectively LiOHH 2o, Li 2cO 3, LiNO 3, MnO 2, Mn (NO 3) 2, MnCO 3, Mn (CH 3cOO) 24H 2o, hydrated manganese dioxide, Mn 2o 3deng, grinding or ball milling evenly after carry out high temperature sintering.The method technique is simple, be applicable to commercially producing, but the synthesis in solid state time is longer, consumes energy high, particle size skewness, and be difficult to the target product of preparative chemistry metering ratio, chemical property is poor.Therefore, improve the electrochemical stability performance of lithium manganate having spinel structure positive electrode, the composition and the preparation technology that optimize manganate cathode material for lithium become current important process.
Summary of the invention
The object of the invention is to for anode material for lithium-ion batteries lithium manganate having spinel structure (LiMn 2o 4) shortcoming of electrochemistry cycle performance difference, a kind of bulk phase-doped modified spinel-type lithium-ion cell positive material LiMn is provided 2-3xm (II) xal xsi xo 4and preparation method thereof, the wherein bivalent metal ion such as M (II)=Mg, Ni, Co, Zn, Cu.This anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4there is higher specific discharge capacity and excellent stable circulation performance, high rate charge-discharge demand can be met, its preparation method overcomes solid-phase synthesis preparation time length, is difficult to control stoichiometric proportion, the shortcomings such as particle size skewness and chemical property difference, the product purity of preparation is high, chemical homogeneous is high, crystalline quality is high, product grain is tiny and be evenly distributed, excellent electrochemical performance and low cost of manufacture.
Technical scheme of the present invention is: anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4, it is characterized in that, the biomolecule expressions of described anode material for lithium-ion batteries is LiMn 2-3xm (II) xal xsi xo 4, the wherein bivalent metal ion such as M (II)=Mg, Ni, Co, Zn, Cu, 0≤x≤0.15.
Anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, comprise the following steps:
Step 1. by lithium source raw material and complexing agent citric acid in molar ratio 1:1 be dissolved in appropriate amount of deionized water, and be placed in 50 DEG C of water-baths and stir, make it dissolve to obtain solution A completely;
Step 2. by manganese source raw material, doping divalent metal element raw material and aluminium source raw material in molar ratio Mn:M (II): Al=(2-3x): x:x is dissolved in appropriate amount of deionized water, obtains solution B;
Silicon source raw material with doping divalent metal element raw material equimolar ratio is dissolved in appropriate absolute ethyl alcohol or deionized water by step 3., obtains alcoholic solution or the suspension-turbid liquid C of silicon source raw material;
Step 2,3 gained solution B, alcoholic solution or suspension-turbid liquid C dropwise instill in step 1 gained solution A by step 4. simultaneously lentamente, and constantly stirring obtains mixed solution.
Step 5. is to step 4 gained mixed solution and dripping ammoniacal liquor, and adjust ph is 6 ~ 8, is warming up to 70 DEG C after stirring 30min, is constantly stirred to moisture evaporation, forms rufous gel;
Step 5 gained rufous gel is put in air dry oven by step 6., and at 110 DEG C ~ 120 DEG C, dry 24h obtains xerogel;
Step 6 gained xerogel is put in Muffle furnace by step 7., and at 400 DEG C ~ 450 DEG C, low temperature presintering 4h ~ 6h obtains intermediate product;
Step 8. by after the grinding evenly of step 7 gained intermediate product at 700 DEG C ~ 850 DEG C high-temperature roasting 12h ~ 18h can obtain spinel-type lithium-ion cell positive material LiMn 2-3xm (II) xal xsi xo 4.
In step 1, described lithium source raw material is at least one in lithium acetate, lithium carbonate, lithium nitrate, lithium citrate, lithium oxalate and lithium hydroxide.
In step 2, described manganese source raw material is at least one in the hydroxide of manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate and manganese and oxide (chemical manganese bioxide and electrolytic manganese dioxide).
In step 2, described doping divalent metal element raw material is at least one in the acetate of corresponding doped chemical, carbonate, nitrate, oxalates and hydroxide and oxide.
In step 2, described aluminium source raw material is at least one in aluminum nitrate, aluminium chloride, aluminum sulfate.
In step 3, described silicon source raw material is at least one in tetraethoxysilane, silicon dioxide, silicic acid and silicate; If select tetraethoxysilane to be silicon source raw material, adopt Organic Alcohol as solvent, prepare to obtain the Organic Alcohol solution of tetraethoxysilane; If at least one in selection silicon dioxide, silicic acid and silicate is as silicon source raw material, adopt deionized water as solvent, prepare and to obtain corresponding suspension-turbid liquid.
In step 4, the mol ratio of described lithium source raw material, manganese source raw material, doping divalent metal element raw material, aluminium source raw material and silicon source raw material is Li:Mn:M (II): Al:Si=(1 ~ 1.1): (2-3x): x:x:x.
The present invention obtains anode material for lithium-ion batteries LiMn by waiting mole manganese element that doping quadrivalent element, triad and diad replace in positive electrode simultaneously 2-3xm (II) xal xsi xo 4.Aluminium is III Main Group Metal Elements, and its valence state is+3 valencys, and the manganese element that trivalent aluminium ion replaces in positive electrode can reduce Mn 3+amount, reduce Jahn-Teller effect to the impact of cathode material structure, be conducive to the structural stability and the electrochemistry cycle performance that improve positive electrode.Silicon is IV main group nonmetalloid, and its valence state is+4 valencys, and the introducing of tetravalence silicon ion has following benefit: (1) silicon ion add the conductivity can optimizing fertile material, improve its high rate during charging-discharging; (2) because the silicon ion of doping is in+4 valencys, higher than average valence+3.5 valency of manganese in fertile material, silicon ion doping After-market fertile material presents n-type semiconductor character, not only can suppress the dissolving of manganese ion under high temperature, the conductivity of positive electrode and the redox property of manganese ion can also be increased, the chemical property of positive electrode is better played; (3) due to+4 valency silicon ions ,+3 valency aluminium ions and+divalent doped metal ion such as are at mole doping, Mn in fertile material 4+/ Mn 3+(mol ratio) is greater than 1, can effectively suppress Jahn-Teller effect.In addition, element silicon has very strong structure effect and temperature effect, and doping is added tetravalence element silicon and is conducive to reducing sintering temperature, improves the structural stability of positive electrode, increases the cycle life of positive electrode.
The present invention adopts sol-gal process to prepare anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4, the wherein bivalent metal ion such as M (II)=Mg, Ni, Co, Zn, Cu.Compared with solid phase method, the chemical reaction of sol-gal process easily carries out, and only needs lower synthesis temperature, it is generally acknowledged that diffusion of components in sol-gel system is in nanometer range, and in solid phase reaction process, the diffusion of each component is in micrometer range.
In sum, tool of the present invention has the following advantages:
1, the present invention adopts sol-gal process technique, and by organic complexing agent, metal ion is fixed, reaction raw materials mixes, and overcomes the shortcoming of conventional solid synthetic method, and the product crystalline quality of preparation is excellent, chemical uniformity good, particle is tiny, purity is high.
2, the spinel-type lithium-ion cell positive material LiMn for preparing of the present invention 2-3xm (II) xal xsi xo 4in ,+divalent doped metallic elements ,+3 valency aluminium elements and+4 valency element silicons add by equimolar ratio example, fully by means of the advantage of each doped chemical, can improve the combination property of positive electrode.
3, the spinel-type lithium-ion cell positive material LiMn for preparing of the present invention 2-3xm (II) xal xsi xo 4there is higher specific discharge capacity and excellent stable circulation performance, be applicable to high rate charge-discharge demand; Under room temperature environment, when constant current charge-discharge multiplying power is 0.5C, the first discharge specific capacity of this spinel-type lithium-ion cell positive material can reach 123.4mAh/g, and circulate and still can reach 120.5 50 times later, capability retention is up to 97.6%.
4, in technique of the present invention, reaction raw material used are all general chemical products, abundance, low price, low cost of manufacture.
5, in technique of the present invention, device therefor is simple, produces, both met environmental protection concept in preparation process without poisonous and harmful substance, is easy to again to realize large-scale industrial and produces.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4process chart.
Fig. 2 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4xRD figure.
Fig. 3 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4sEM figure.
Fig. 4 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4first charge-discharge curve chart under 0.5C multiplying power.
Fig. 5 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4cycle performance curve chart under 0.5C multiplying power.
Fig. 6 is that the present invention prepares anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4coulombic efficiency curve chart under 0.5C multiplying power.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
0.0525mol (2.2029g) lithium hydroxide and 0.0525mol (11.0324g) citric acid are dissolved in appropriate amount of deionized water, and are placed in 50 DEG C of water-baths and stir, make it dissolve completely and obtain solution A; 0.0925mol (22.6708g) manganese acetate, 0.0025mol (0.6410g) magnesium nitrate and 0.0025mol (0.9378g) aluminum nitrate are dissolved in deionized water and prepare to obtain mixed salt solution B; 0.0025mol (0.5469g) tetraethoxysilane is dissolved in the ethanolic solution C that appropriate absolute ethyl alcohol obtains tetraethoxysilane.
Dropwise being added in solution A lentamente by the ethanolic solution C of mixed salt solution B and tetraethoxysilane simultaneously, and constantly stir, is 8 by ammoniacal liquor adjust ph, is warming up to 70 DEG C after stirring 30min, and till continuing to be stirred to generation rufous gel; Then the rufous gel 110 DEG C of dry 24h in air dry oven will obtained, then be put in 450 DEG C of low temperature presintering 4h in Muffle furnace; Finally the intermediate product that obtain is taken out grinding, to be put in Muffle furnace pre-burning 18h at 750 DEG C of temperature and can to obtain spinel-type lithium-ion cell positive material LiMn 1.85mg 0.05al 0.05si 0.05o 4.
To the anode material for lithium-ion batteries LiMn of preparation 1.85mg 0.05al 0.05si 0.05o 4carry out constant current charge-discharge test, can find out that this positive electrode has higher specific discharge capacity and excellent stable circulation performance from test result, be applicable to high rate charge-discharge demand; Under room temperature environment, when constant current charge-discharge multiplying power is 0.5C, the first discharge specific capacity of this spinel-type lithium-ion cell positive material can reach 123.4mAh/g, and circulate and still can reach 120.5 50 times later, capability retention is up to 97.6%.
Embodiment two:
0.0263mol (1.1015g) lithium hydroxide and 0.0263mol (5.5162g) citric acid are dissolved in appropriate amount of deionized water, and are placed in 50 DEG C of water-baths and stir, make it dissolve completely and obtain solution A; 0.0463mol (11.3354g) manganese acetate, 0.0013mol (0.2744g) zinc acetate and 0.0013mol (0.4689g) aluminum nitrate are dissolved in deionized water and prepare to obtain mixed salt solution B; 0.0013mol (0.2735g) tetraethoxysilane is dissolved in the ethanolic solution C that appropriate absolute ethyl alcohol obtains tetraethoxysilane.
Dropwise being added in solution A lentamente by the ethanolic solution C of mixed salt solution B and tetraethoxysilane simultaneously, and constantly stir, is 8 by ammoniacal liquor adjust ph, is warming up to 70 DEG C after stirring 30min, and till continuing to be stirred to generation rufous gel; Then the rufous gel 110 DEG C of dry 24h in air dry oven will obtained, then be put in 450 DEG C of low temperature presintering 4h in Muffle furnace; Finally the intermediate product that obtain is taken out grinding, to be put in Muffle furnace pre-burning 18h at 750 DEG C of temperature and can to obtain spinel-type lithium-ion cell positive material LiMn 1.85zn 0.05al 0.05si 0.05o 4, its effect and performance substantially the same manner as Example 1.

Claims (10)

1. anode material for lithium-ion batteries LiMn 2-3xm (II) xal xsi xo 4, it is characterized in that, the biomolecule expressions of described anode material for lithium-ion batteries is LiMn 2-3xm (II) xal xsi xo 4, wherein M (II)=Mg, Ni, Co, Zn, Cu, 0≤x≤0.15.
2. by anode material for lithium-ion batteries LiMn described in claim 1 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, comprise the following steps:
Step 1. by lithium source raw material and complexing agent citric acid in molar ratio 1:1 be dissolved in appropriate amount of deionized water, and be placed in 50 DEG C of water-baths and stir, make it dissolve to obtain solution A completely;
Step 2. by manganese source raw material, doping divalent metal element raw material and aluminium source raw material in molar ratio Mn:M (II): Al=(2-3x): x:x is dissolved in appropriate amount of deionized water, obtains solution B;
Silicon source raw material with doping divalent metal element raw material equimolar ratio is dissolved in appropriate absolute ethyl alcohol or deionized water by step 3., obtains alcoholic solution or the suspension-turbid liquid C of silicon source raw material;
Step 2,3 gained solution B, alcoholic solution or suspension-turbid liquid C dropwise instill in step 1 gained solution A by step 4. simultaneously lentamente, and constantly stirring obtains mixed solution;
Step 5. is to step 4 gained mixed solution and dripping ammoniacal liquor, and adjust ph is 6 ~ 8, is warming up to 70 DEG C after stirring 30min, is constantly stirred to moisture evaporation, forms rufous gel;
Step 5 gained rufous gel is put in air dry oven by step 6., and at 110 DEG C ~ 120 DEG C, dry 24h obtains xerogel;
Step 6 gained xerogel is put in Muffle furnace by step 7., and at 400 DEG C ~ 450 DEG C, low temperature presintering 4h ~ 6h obtains intermediate product;
Step 8. by after the grinding evenly of step 7 gained intermediate product at 700 DEG C ~ 850 DEG C high-temperature roasting 15h ~ 24h can obtain spinel-type lithium-ion cell positive material LiMn 2-3xm (II) xal xsi xo 4.
3. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 4, the mol ratio of described lithium source raw material, manganese source raw material, adulterate divalent metal element raw material, aluminium source raw material and silicon source raw material is Li:Mn:M (II): Al:Si=(1 ~ 1.1): (2-3x): x:x:x.
4. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 1, described lithium source raw material is at least one in lithium acetate, lithium carbonate, lithium nitrate, lithium citrate, lithium oxalate and lithium hydroxide.
5. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 2, described manganese source raw material is at least one in the hydroxide of manganese acetate, manganese carbonate, manganese nitrate, manganese oxalate and manganese and oxide (chemical manganese bioxide and electrolytic manganese dioxide).
6. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 2, described doping divalent metal element raw material is at least one in the acetate of corresponding doped chemical, carbonate, nitrate, oxalates and hydroxide and oxide.
7. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 2, described aluminium source raw material is at least one in aluminum nitrate, aluminium chloride, aluminum sulfate.
8. by anode material for lithium-ion batteries LiMn described in claim 2 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, in step 3, described silicon source raw material is at least one in tetraethoxysilane, silicon dioxide, silicic acid and silicate.
9. by anode material for lithium-ion batteries LiMn described in claim 8 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, described silicon source raw material is tetraethoxysilane, adopts Organic Alcohol as solvent, prepares to obtain the Organic Alcohol solution of tetraethoxysilane.
10. by anode material for lithium-ion batteries LiMn described in claim 8 2-3xm (II) xal xsi xo 4preparation method, it is characterized in that, described silicon source raw material is at least one in silicon dioxide, silicic acid and silicate, adopts deionized water as solvent, prepares and to obtain corresponding suspension-turbid liquid.
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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