CN103337620B - Anode material for lithium-ion batteries and preparation method thereof - Google Patents
Anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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Abstract
A preparation method for anode material for lithium-ion batteries, comprises step: stoichiometrically, value Mn salt, at a low price manganese salt and oxidant is dissolved in deionized water for stirring and mixes, obtain mixed liquor; Described mixed liquor is carried out hydro-thermal reaction to obtain slurries; Described slurries are carried out filtration washing, drying, obtains δ-MnO
2nanometer sheet material; According to stoichiometric proportion by lithium salts and described δ-MnO
2nanometer sheet material mixes, and obtains mixture; By drying at room temperature after uniform stirring in described mixture input organic solution, obtain powder; And after described powder being sintered in oxidizing atmosphere, obtain anode material for lithium-ion batteries through washing, dry also grinding.The present invention also provides described anode material for lithium-ion batteries.Anode material for lithium-ion batteries provided by the invention has the feature of good cycle.
Description
Technical field
The present invention relates to lithium ion battery material technical field, particularly a kind of flake nano structure lithium ion battery positive electrode and preparation method thereof.
Background technology
Along with the development of the mankind, energy crisis and environmental problem highlight day by day, and new energy storage device obtains the attention of people.In recent years, lithium ion battery because its specific energy is high, quality is light, advantages of environment protection occupies energy storage device gradually staple market.As the original paper storing lithium ion in lithium ion battery, the performance of positive electrode to lithium ion battery plays important effect.Therefore, develop the positive electrode possessing excellent electrochemical performance and become one of important means improving lithium ion battery overall performance.
Current commercial li-ion cell positive material is based on cobalt acid lithium, but this material price is higher, and the pollution problem of cobalt ions is not yet effectively solved.LiMn2O4 (LiMn
2o
4) become one of substitution material of cobalt acid lithium because of advantages such as its cost are low, security performance good, environmental friendliness, energy force density are large.Common lithium manganate material crystal structure is mainly spinel-type, micromorphology is regular octahedron shape particle, can be obtained by conventional methods such as soft chemical method, microwave sintering method, emulsification seasoning, sol-gal process, high temperature solid-state method, coprecipitation, hydro thermal method or ultrasonic wave sputtering methods.But, lithium manganate having spinel structure is due to reasons such as manganese ion dissolution, electrolytic corrosion, Jahn-Teller effects structural stabilities, its lithium ion transport passage is damaged, capacity attenuation is very fast, cycle performance is deteriorated, and limits LiMn2O4 as the development of anode material for lithium-ion batteries and application.Therefore, Scientific Research Workers have carried out further exploration to its method of modifying, as coated, doping, nano material are prepared, thus prepared the manganate cathode material for lithium of electrochemical performance.Wherein, novel nano structure material is owing to can provide shorter lithium ion transport passage and larger surface area, and one of focus becoming research.
Summary of the invention
Therefore, be necessary the anode material for lithium-ion batteries that a kind of good cycle is provided, and a kind of preparation method of eco-friendly described anode material for lithium-ion batteries is provided.
A preparation method for anode material for lithium-ion batteries, comprises step: stoichiometrically, value Mn salt, at a low price manganese salt and oxidant is dissolved in deionized water for stirring and mixes, obtain mixed liquor; Described mixed liquor is carried out hydro-thermal reaction to obtain slurries; Described slurries are carried out filtration washing, drying, obtains δ-MnO
2nanometer sheet material; According to stoichiometric proportion by lithium salts and described δ-MnO
2nanometer sheet material mixes, and obtains mixture; By drying at room temperature after uniform stirring in described mixture input organic solution, obtain powder; And after sintering described powder in oxidizing atmosphere, obtain anode material for lithium-ion batteries through washing, dry also grinding, this anode material for lithium-ion batteries is LiMn2O4 nanometer sheet.
A kind of anode material for lithium-ion batteries, this anode material for lithium-ion batteries is made up of the preparation method of described anode material for lithium-ion batteries, it is made up of LiMn2O4 nanometer sheet, the thickness of described LiMn2O4 nanometer sheet is 10nm-50nm, and length and the width of described LiMn2O4 nanometer sheet reach 200nm-500nm.
A kind of anode material for lithium-ion batteries, it is made up of the preparation method of described anode material for lithium-ion batteries.
Compared with prior art, the anode material for lithium-ion batteries that the technical program provides, it is made up of LiMn2O4 nanometer sheet, LiMn2O4 nanometer sheet can provide shorter lithium ion transport passage and larger specific area, thus improve lithium ion diffusivity in the material, thus further increase the cycle performance of nanoscale twins lithium manganate material.Described method for preparing anode material of lithium-ion battery technique is simple, and implementation cost is low, is easy to realize industrialization, and without noxious substance, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the XRD figure of anode material for lithium-ion batteries prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM figure of anode material for lithium-ion batteries prepared by the embodiment of the present invention 1.
Fig. 3 is the cycle performance curve of anode material for lithium-ion batteries prepared by the embodiment of the present invention 1.
Main element symbol description
Nothing
Following embodiment will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Below, illustrate that the technical program provides anode material for lithium-ion batteries and preparation method thereof with specific embodiment.
The technical program provides a kind of preparation method of anode material for lithium-ion batteries, comprises step:
The first step, stoichiometrically, dissolves in deionized water for stirring successively by value Mn salt, at a low price manganese salt and oxidant and mixes, obtain mixed liquor.
In this step, described stoichiometric proportion is relevant with the value Mn salt of employing, the at a low price concrete material of manganese salt and oxidant, namely according to the various materials that reality adopts, according to chemical equation proportioning when value Mn salt, at a low price manganese salt and oxidant reaction generation manganese dioxide, carry out the consumption calculating value Mn salt, at a low price manganese salt and oxidant.Described value Mn salt is permanganate or permanganic acid salt solution and crystal.Value Mn salt is specifically as follows high manganese lithium, sodium permanganate, potassium permanganate, ammonium permanganate, acerdol, barium permanganate, zinc permanganate, magnesium permanganate, copper permanganate, silver permanganate, permanganic acid tin, high manganese lithium water and crystal, sodium permanganate water and crystal, potassium permanganate water and crystal, ammonium permanganate water and crystal, acerdol water and crystal, barium permanganate water and crystal, zinc permanganate water and crystal, magnesium permanganate water and crystal, copper permanganate water and crystal, at least one in silver permanganate water and crystal and permanganic acid Xi Shui and crystal etc.Described low price manganese salt is manganous salt or is bivalent manganese salt solution and crystal.Described low price manganese salt is specifically as follows at least one in manganese sulfate, manganese chloride, manganese nitrate, hypochlorous acid manganese, manganese acetate water and crystal, manganese sulfate water and crystal, manganese chloride water and crystal, manganese nitrate water and crystal, hypochlorous acid manganese water and crystal and manganese acetate water and crystal etc.Described oxidant is have the oxidant compared with strong oxidizing property, is specifically as follows at least one in potassium chlorate, hydrogen peroxide, ammonium persulfate, Peracetic acid, nitric acid, sulfuric acid, clorox and SODIUM PERCARBONATE.In this step, preferably, value Mn salt, at a low price manganese salt and oxidant are dissolved in water successively and stirs 10 minutes to 60 minutes, make to mix.Described water is preferably deionized water.
Second step, carries out hydro-thermal reaction to obtain slurries by described mixed liquor.
In this step, the described mixed liquor that the first step can be obtained is poured in hydro-thermal tank prepared by polytetrafluoroethylene, puts into explosion-proof baking oven with after stainless steel tube sealing.With 1-20 centigrade per minute (DEG C min
-1) programming rate be heated to 100 DEG C-160 DEG C, insulation 2-5 days, be then cooled to room temperature with the cooldown rate of 1-20 DEG C/min.
Described slurries are carried out filtration washing by the 3rd step, dry afterwards, obtain δ-MnO
2nanometer sheet material.
In this step, the described slurry obtained with deionized water multiple times of filtration washing second step, then puts into baking oven by the product obtained after washing dry, obtains δ-MnO
2nanometer sheet material.Described δ-MnO
2nanometer sheet is the follow-up presoma for making anode material for lithium-ion batteries.
4th step, according to stoichiometric proportion by lithium salts and described δ-MnO
2nanometer sheet material mixes, and obtains mixture.
In this step, described lithium salts is at least one in lithium carbonate, lithium acetate, lithium hydroxide, lithium nitrate, lithium oxalate, ethylenediamine tetra-acetic acid lithium salts and carbamyl phosphate dilithium salt.The stoichiometric proportion of this step is according to lithium salts and δ-MnO
2the stoicheiometry that nanometer sheet carries out the chemical equation of chemical reaction generation LiMn2O4 carries out calculating lithium salts and described δ-MnO
2the consumption of nanometer sheet material.
5th step, by drying at room temperature after uniform stirring in described mixture input organic solution, obtains powder.
In this step, described organic solution is at least one in acetone, ethanol, methyl alcohol, chlorination ethanol, dichloroethanes, butanols, dimethylbenzene, amyl acetate and isopropylbenzene.Being dropped into described mixture in organic solution after uniform stirring after drying at room temperature, dried mixture to be fed in organic solution drying at room temperature after uniform stirring, to obtain powder also repeated multiple timesly.
6th step, to after described powder sintering in oxidizing atmosphere, obtains LiMn2O4 nanometer sheet through washing, dry also grinding, namely obtains described anode material for lithium-ion batteries.
In this step, described powder is placed in vacuum tube furnace, in oxidizing atmosphere, is heated to uniform temperature and is incubated some hours, the cold rear deionized water multiple times of filtration washing of stove.Particularly, described powder is placed in vacuum tube furnace, in oxidizing atmosphere, is heated to 400-800 DEG C with the programming rate of 2-8 DEG C/min, insulation 10-30 hour, the cold rear deionized water multiple times of filtration washing of stove, then dry 1-100 hour.Described oxidizing atmosphere for pass at least one in air atmosphere or oxygen atmosphere in vacuum tube furnace.Afterwards, grind, obtain LiMn2O4 nanometer sheet, namely obtain described anode material for lithium-ion batteries.
Described anode material for lithium-ion batteries is made up of LiMn2O4 nanometer sheet, and the thickness of described LiMn2O4 nanometer sheet is 10nm-50nm, and length and the width of described LiMn2O4 nanometer sheet can reach 200nm-500nm respectively.
Be understandable that, the size of described LiMn2O4 nanometer sheet can be controlled by each reaction time in adjustment preparation method and reaction temperature.
Below, the preparation method of described anode material for lithium-ion batteries is illustrated with multiple embodiment.
Embodiment 1:
5.26 grams of (g) potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100 milliliters of (mL) deionized water for stirring 30 minutes (min) successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 degrees Celsius (DEG C) insulation, 48 hours (h) by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 400 DEG C sintering 10 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 2:
5.26g potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 130 DEG C of insulation 72h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 500 DEG C sintering 15 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 3:
5.26g potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 160 DEG C of insulation 96h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 600 DEG C sintering 20 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 4:
5.26g potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 DEG C of insulation 120h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 700 DEG C sintering 25 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 5:
5.20g ammonium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 DEG C of insulation 48h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 400 DEG C sintering 10 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.The present embodiment is identical with condition with embodiment 1 process, just adopts ammonium permanganate to be value Mn salt.
Embodiment 6:
5.26g potassium permanganate, 0.26g manganese nitrate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 DEG C of insulation 48h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 400 DEG C sintering 10 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 7:
5.26g potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 DEG C of insulation 48h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2powder.According to stoichiometric proportion, lithium hydroxide and manganese dioxide nano-plates are mixed in absolute ethyl alcohol, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 400 DEG C sintering 10 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Embodiment 8:
5.26g potassium permanganate, 0.56g manganese sulfate and appropriate ammonium persulfate are dissolved in 100mL deionized water for stirring 30min successively; Gained darkviolet mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, put into explosion-proof baking oven with after stainless steel tube sealing; Be 100 DEG C of insulation 48h by explosion-proof baking oven optimum configurations; After having reacted, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, controlling bake out temperature is 80 DEG C, obtains δ-MnO
2nanometer sheet.According to stoichiometric proportion, lithium acetate and manganese dioxide nano-plates are mixed in anhydrous propanone, and uniform stirring; At room temperature under condition, drying is carried out to gained mixture, obtain powder; Powder is placed in vacuum tube furnace 400 DEG C sintering 10 hours; After product spends deionized water filtering drying, relevant nanometer sheet LiMn2O4 LiMn can be obtained
2o
4material.
Refer to Fig. 1, Fig. 1 is the XRD figure that the technical program embodiment 1 obtains LiMn2O4 nanometer sheet.As seen from Figure 1, the material composition that the technical program is obtained is LiMn2O4.The collection of illustrative plates that the technical program obtains LiMn2O4 nanometer sheet is consistent with the standard diagram of LiMn2O4.
Adopt electronic scanner microscope to observe LiMn2O4 nanometer sheet obtained for embodiment 1, obtain photo as shown in Figure 2, can be drawn by Fig. 2, the LiMn2O4 nanometer sheet obtained is lamellar structure.
The LiMn2O4 nanometer sheet that the technical program embodiment 1 obtains is as the positive pole of lithium ion battery, and the cycle performance curve obtained is shown in as shown in curve A in Fig. 3.Common lithium acid manganese (lithium manganate having spinel structure) as anode material for lithium-ion batteries cycle performance as curveb.Can draw, the LiMn2O4 nanometer sheet that the technical program obtains obviously is better than common LiMn2O4.
The anode material for lithium-ion batteries that the technical program provides, it is made up of LiMn2O4 nanometer sheet structure, nanoscale twins LiMn2O4 structure can provide shorter lithium ion transport passage and larger specific area, thus improve lithium ion diffusivity in the material, thus further increase the cycle performance of nanoscale twins lithium manganate material.
Described method for preparing anode material of lithium-ion battery technique is simple, and implementation cost is low, is easy to realize industrialization, and without noxious substance, environmental friendliness.
Be understandable that, for the person of ordinary skill of the art, other various corresponding change and distortion can be made by technical conceive according to the present invention, and all these change the protection range that all should belong to the claims in the present invention with distortion.
Claims (11)
1. a preparation method for anode material for lithium-ion batteries, comprises step:
Stoichiometrically, value Mn salt, at a low price manganese salt and oxidant are dissolved in deionized water for stirring and mixes, obtain mixed liquor;
Described mixed liquor is carried out hydro-thermal reaction to obtain slurries;
Described slurries are carried out filtration washing, drying, obtains δ-MnO
2nanometer sheet material;
According to stoichiometric proportion by lithium salts and described δ-MnO
2nanometer sheet material mixes, and obtains mixture;
By drying at room temperature after uniform stirring in described mixture input organic solution, obtain powder; And
After sintering described powder in oxidizing atmosphere, obtain anode material for lithium-ion batteries through washing, dry also grinding, this anode material for lithium-ion batteries is LiMn2O4 nanometer sheet.
2. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, described value Mn salt is permanganate or permanganic acid salt solution and crystal, and described low price manganese salt is manganous salt or bivalent manganese salt solution and crystal.
3. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, described value Mn salt is high manganese lithium, sodium permanganate, potassium permanganate, ammonium permanganate, acerdol, barium permanganate, zinc permanganate, magnesium permanganate, copper permanganate, silver permanganate, permanganic acid tin, high manganese lithium water and crystal, sodium permanganate water and crystal, potassium permanganate water and crystal, ammonium permanganate water and crystal, acerdol water and crystal, barium permanganate water and crystal, zinc permanganate water and crystal, magnesium permanganate water and crystal, copper permanganate water and crystal, at least one in silver permanganate water and crystal and permanganic acid Xi Shui and crystal, described low price manganese salt is manganese sulfate, manganese chloride, manganese nitrate, hypochlorous acid manganese, manganese acetate water and crystal, manganese sulfate water and crystal, manganese chloride water and crystal, manganese nitrate water and crystal, at least one in hypochlorous acid manganese water and crystal and manganese acetate water and crystal, described oxidant is potassium chlorate, hydrogen peroxide, ammonium persulfate, Peracetic acid, nitric acid, sulfuric acid, at least one in clorox and SODIUM PERCARBONATE.
4. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, described mixed liquor is carried out hydro-thermal reaction and comprises with the method obtaining slurries:
Described mixed liquor is poured in hydro-thermal tank prepared by polytetrafluoroethylene, explosion-proof baking oven is put into after sealing described hydro-thermal tank with stainless steel tube, be heated to 100 DEG C-160 DEG C with the programming rate of 1-20 DEG C/min, insulation 2-5 days, is then cooled to room temperature with the cooldown rate of 1-20 DEG C/min.
5. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, described lithium salts is at least one in lithium carbonate, lithium acetate, lithium hydroxide, lithium nitrate, lithium oxalate, ethylenediamine tetra-acetic acid lithium salts and carbamyl phosphate dilithium salt.
6. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, comprise in oxidizing atmosphere to the method that described powder processes:
Described powder is placed in vacuum tube furnace, in oxidizing atmosphere, is heated to 400-800 DEG C with the programming rate of 2-8 DEG C of min-1, keep after 10-30 hour, the cold rear deionized water multiple times of filtration washing gained powder of stove, then dry 1-100 hour.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 6, it is characterized in that, described oxidizing atmosphere for pass at least one in air atmosphere or oxygen atmosphere in vacuum tube furnace.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, described organic solution is at least one in acetone, ethanol, methyl alcohol, chlorination ethanol, dichloroethanes, butanols, dimethylbenzene, amyl acetate and isopropylbenzene.
9. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, described mixture being dropped in organic solution after uniform stirring after drying at room temperature, dried mixture to be fed in organic solution drying at room temperature after uniform stirring, to obtain powder also repeated multiple timesly.
10. an anode material for lithium-ion batteries, this anode material for lithium-ion batteries is made up of the preparation method of the anode material for lithium-ion batteries as described in any one of claim 1 to 9, it is made up of LiMn2O4 nanometer sheet, the thickness of described LiMn2O4 nanometer sheet is 10nm-50nm, and length and the width of described LiMn2O4 nanometer sheet reach 200nm-500nm.
11. 1 kinds of anode material for lithium-ion batteries, it is made up of the preparation method of the anode material for lithium-ion batteries as described in any one of claim 1 to 9.
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| CN103641174B (en) * | 2013-12-10 | 2015-10-07 | 中国科学院宁波材料技术与工程研究所 | Nano-sheet MnO 2-graphene composite material, its preparation method and ultracapacitor |
| CN107915260B (en) * | 2017-11-30 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of nano MnO2 particles with high transition entropy |
| CN109037613B (en) * | 2018-07-04 | 2021-04-16 | 上海电气集团股份有限公司 | Ruthenium dioxide coated spinel lithium-rich lithium manganate and preparation method thereof |
| CN113839029B (en) * | 2020-06-24 | 2023-10-17 | 深圳市比亚迪锂电池有限公司 | Lithium-manganese battery |
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| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
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