CN103337620A - Positive pole material of lithium ion battery and preparation method thereof - Google Patents
Positive pole material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103337620A CN103337620A CN2013102222774A CN201310222277A CN103337620A CN 103337620 A CN103337620 A CN 103337620A CN 2013102222774 A CN2013102222774 A CN 2013102222774A CN 201310222277 A CN201310222277 A CN 201310222277A CN 103337620 A CN103337620 A CN 103337620A
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Abstract
The invention relates to a preparation method of a positive pole material of a lithium ion battery. The preparation method comprises the following steps of: dissolving a high-valence manganese salt, a low-valence manganese salt and an oxidant in deionized water according to the stoichiometric ratio, stirring and uniformly mixing to get a mixed solution; performing hydrothermal reaction on the mixed solution to get slurry; filtering, washing and drying the slurry to get a delta-MnO2 nano-sheet material; uniformly mixing a lithium salt and the delta-MnO2 nano-sheet material according to the stoichiometric ratio to get a mixture; putting the mixture into an organic solvent, uniformly stirring, and then drying at room temperature to get powder; sintering the powder in an oxidizing atmosphere, washing, drying and grinding to get the positive pole material of the lithium ion battery. The invention further provides the positive pole material of the lithium ion battery. The positive pole material of the lithium ion battery, provided by the invention, has the characteristic of good cycling performance.
Description
Technical field
The present invention relates to the 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 mankind's development, energy crisis and environmental problem highlight day by day, and new energy storage device obtains people's attention.In recent years, lithium ion battery is because of its specific energy height, quality are light, advantages of environment protection occupies energy storage device gradually staple market.As the original paper that stores lithium ion in the lithium ion battery, positive electrode plays important effect to the performance of lithium ion battery.Therefore, develop the positive electrode that possesses excellent electrochemical performance and become one of important means that improves the lithium ion battery overall performance.
Present commercial li-ion cell positive material is based on cobalt acid lithium, yet this material price is higher, and the pollution problem of cobalt ions is effectively solved as yet.LiMn2O4 (LiMn
2O
4), security performance low because of its cost is good, environmental friendliness, advantage such as can force density big become one of substitution material of cobalt acid lithium.Common lithium manganate material crystal structure is mainly spinel-type, the microcosmic surface pattern is regular octahedron shape particle, can obtain 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.Yet, lithium manganate having spinel structure is owing to reasons such as manganese ion dissolving, electrolyte burn into Jahn-Teller effects structural stabilities, its lithium ion transmission channel is damaged, capacity attenuation is very fast, the cycle performance variation has limited development and the application of LiMn2O4 as anode material for lithium-ion batteries.Therefore, research work personnel have carried out further exploration to its method of modifying, as coating, doping, nano material preparation etc., thereby prepare the manganate cathode material for lithium of chemical property excellence.Wherein, the novel nano structural material be owing to can provide short lithium ion transmission channel and bigger surface area, and becomes one of focus of research.
Summary of the invention
Therefore, be necessary to provide a kind of anode material for lithium-ion batteries of good cycle, and a kind of preparation method of eco-friendly described anode material for lithium-ion batteries is provided.
A kind of preparation method of anode material for lithium-ion batteries comprises step: by stoichiometric proportion, high price manganese salt, low price manganese salt and oxidant are dissolved in deionized water for stirring mix, obtain mixed liquor; Described mixed liquor is carried out hydro-thermal reaction to obtain slurries; Described slurries are carried out filtration washing, drying, obtain δ-MnO
2The nanometer sheet material; According to stoichiometric proportion with lithium salts and described δ-MnO
2The nanometer sheet material mixes, and obtains mixture; Described mixture is dropped into the even back drying at room temperature that stirs in the organic solution, obtain powder; And after in oxidizing atmosphere, described powder being carried out sintering, through washing, dry and grind and obtain anode material for lithium-ion batteries.
A kind of anode material for lithium-ion batteries, it is made of the LiMn2O4 nanometer sheet, and the thickness of described LiMn2O4 nanometer sheet is 10 nm-50nm, and length and the width of described LiMn2O4 nanometer sheet reach 200nm-500nm.
A kind of anode material for lithium-ion batteries, its preparation method by described anode material for lithium-ion batteries makes.
Compared with prior art, the anode material for lithium-ion batteries that the technical program provides, it is made up of the LiMn2O4 nanometer sheet, the LiMn2O4 nanometer sheet can provide than short lithium ion transmission channel and bigger specific area, thereby improve the diffusivity of lithium ion in material, thereby further improved the cycle performance of nanometer lamella lithium manganate material.Described method for preparing anode material of lithium-ion battery technology is simple, and implementation cost is low, is easy to realize industrialization, and does not have noxious substance, environmental friendliness.
Description of drawings
Fig. 1 is the XRD figure of the anode material for lithium-ion batteries of the embodiment of the invention 1 preparation.
Fig. 2 is the SEM figure of the anode material for lithium-ion batteries of the embodiment of the invention 1 preparation.
Fig. 3 is the cycle performance curve of the anode material for lithium-ion batteries of the embodiment of the invention 1 preparation.
The main element symbol description
Do not have
Following embodiment will further specify the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Below, illustrate that with specific embodiment the technical program provides anode material for lithium-ion batteries and preparation method thereof.
The technical program provides a kind of preparation method of anode material for lithium-ion batteries, comprises step:
The first step by stoichiometric proportion, is dissolved in deionized water for stirring successively with high price manganese salt, low price manganese salt and oxidant and is mixed, and obtains mixed liquor.
In this step, described stoichiometric proportion is relevant with the concrete material of high price manganese salt, low price manganese salt and the oxidant of employing, i.e. various materials that adopt according to reality, chemical equation proportioning when generating manganese dioxide according to high price manganese salt, low price manganese salt and oxidant reaction is calculated the consumption of manganese salt, low price manganese salt and oxidant at high price.Described high price manganese salt is permanganate or permanganic acid salt solution and crystal.High price manganese 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 a in silver permanganate water and crystal and permanganic acid Xi Shui and the 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 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 the crystal etc. at least a.Described oxidant is the oxidant that has than strong oxidizing property, is specifically as follows in potassium chlorate, hydrogen peroxide, ammonium persulfate, Peracetic acid, nitric acid, sulfuric acid, clorox and the SODIUM PERCARBONATE at least a.In this step, preferably, manganese salt, low price manganese salt and oxidant dissolve in successively in the water and stirred 10 minutes to 60 minutes at high price, make to mix.Described water is preferably deionized water.
In second step, described mixed liquor is carried out hydro-thermal reaction to obtain slurries.
In this step, the described mixed liquor that the first step can be obtained is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing.With 1-20 centigrade per minute (℃ min
-1) programming rate be heated to 100 ℃-160 ℃, be incubated 2-5 days, then the cooldown rate with 1-20 ℃/min is cooled to room temperature.
The 3rd step, described slurries are carried out filtration washing, dry afterwards, obtain δ-MnO
2The nanometer sheet material.
In this step, with the described slurry that second step of deionized water multiple times of filtration washing obtains, it is dry that the product that will obtain after will washing is then put into baking oven, obtains δ-MnO
2The nanometer sheet material.Described δ-MnO
2Nanometer sheet is follow-up for the presoma of making anode material for lithium-ion batteries.
The 4th the step, according to stoichiometric proportion with lithium salts and described δ-MnO
2The nanometer sheet material mixes, and obtains mixture.
In this step, described lithium salts is at least a in lithium carbonate, lithium acetate, lithium hydroxide, lithium nitrate, lithium oxalate, ethylenediamine tetra-acetic acid lithium salts and the carbamyl phosphate dilithium salt.The stoichiometric proportion of this step is according to lithium salts and δ-MnO
2The stoicheiometry that nanometer sheet is carried out the chemical equation of chemical reaction generation LiMn2O4 calculates lithium salts and described δ-MnO
2The consumption of nanometer sheet material.
The 5th step, described mixture is dropped into the even back drying at room temperature that stirs in the organic solution, obtain powder.
In this step, described organic solution is at least a in acetone, ethanol, methyl alcohol, chlorination ethanol, dichloroethanes, butanols, dimethylbenzene, amyl acetate and the isopropylbenzene.After in described mixture input organic solution, evenly stirring the back drying at room temperature, also repeated multiple times dried mixture is fed into and evenly stirs the back drying at room temperature in the organic solution, to obtain powder.
The 6th step to behind the described powder sintering, obtained the LiMn2O4 nanometer sheet through washing, dry also the grinding in oxidizing atmosphere, namely obtain described anode material for lithium-ion batteries.
In this step, described powder is placed vacuum tube furnace, be heated to uniform temperature and be incubated some hours in oxidizing atmosphere, wash with the deionized water multiple times of filtration the cold back of stove.Particularly, described powder is placed vacuum tube furnace, the programming rate with 2-8 ℃/min in oxidizing atmosphere is heated to 400-800 ℃, is incubated 10-30 hour, and the cold back of stove is washed then dry 1-100 hour with the deionized water multiple times of filtration.Described oxidizing atmosphere is at least a in bubbling air atmosphere or the oxygen atmosphere in vacuum tube furnace.Afterwards, grind, obtain the LiMn2O4 nanometer sheet, namely obtain described anode material for lithium-ion batteries.
Described anode material for lithium-ion batteries is made of the LiMn2O4 nanometer sheet, and the thickness of described LiMn2O4 nanometer sheet is 10nm-50 nm, and the length of described LiMn2O4 nanometer sheet and width can reach 200nm-500nm respectively.
Be understandable that the size of described LiMn2O4 nanometer sheet can be controlled by each reaction time and the reaction temperature adjusted among the preparation method.
Below, specify the preparation method of described anode material for lithium-ion batteries with a plurality of embodiment.
Embodiment 1:
5.26 gram (g) potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 milliliters of (mL) deionized water for stirring 30 minutes (min) successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter be set to 100 degrees centigrade (℃) insulation 48 hours (h); After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 400 ℃ of sintering of vacuum tube furnace 10 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 2:
5.26 g potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 130 ℃ of insulation 72 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 500 ℃ of sintering of vacuum tube furnace 15 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 3:
5.26 g potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 160 ℃ of insulation 96 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 600 ℃ of sintering of vacuum tube furnace 20 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 4:
5.26 g potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 100 ℃ of insulation 120 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 700 ℃ of sintering of vacuum tube furnace 25 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 5:
5.20 g ammonium permanganates, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 100 ℃ of insulation 48 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 400 ℃ of sintering of vacuum tube furnace 10 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.Present embodiment is identical with condition with embodiment 1 process, and just adopting ammonium permanganate is high price manganese salt.
Embodiment 6:
5.26 g potassium permanganate, 0.26 g manganese nitrate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 100 ℃ of insulation 48 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 400 ℃ of sintering of vacuum tube furnace 10 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 7:
5.26 g potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 100 ℃ of insulation 48 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Powder.According to stoichiometric proportion lithium hydroxide and manganese dioxide nano-plates are sneaked in the absolute ethyl alcohol, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 400 ℃ of sintering of vacuum tube furnace 10 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
Embodiment 8:
5.26 g potassium permanganate, 0.56 g manganese sulfate and an amount of ammonium persulfate are dissolved in 100 mL deionized water for stirring, 30 min successively; Gained darkviolet mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, with putting into explosion-proof baking oven after the stainless steel tube sealing; Explosion-proof baking oven parameter is set to 100 ℃ of insulation 48 h; After reaction is finished, with deionized water multiple times of filtration washing gained slurry; Product is put into baking oven dry, the control bake out temperature is 80 ℃, obtains δ-MnO
2Nanometer sheet.According to stoichiometric proportion lithium acetate and manganese dioxide nano-plates are sneaked in the anhydrous propanone, and evenly stir; At room temperature under the condition, the gained mixture is carried out drying, obtain powder; Powder was placed 400 ℃ of sintering of vacuum tube furnace 10 hours; After product spends the deionised water filtering drying, can obtain relevant nanometer sheet LiMn2O4 LiMn
2O
4Material.
See also Fig. 1, Fig. 1 makes the XRD figure of LiMn2O4 nanometer sheet for the technical program embodiment 1.As seen from Figure 1, the material composition that makes of the technical program is LiMn2O4.It is consistent with the standard diagram of LiMn2O4 that the technical program makes the collection of illustrative plates of LiMn2O4 nanometer sheet.
The LiMn2O4 nanometer sheet that embodiment 1 is made adopts electronic scanner microscope to observe, and obtains photo as shown in Figure 2, can be drawn by Fig. 2, and the LiMn2O4 nanometer sheet that obtains is lamellar structure.
The LiMn2O4 nanometer sheet that the technical program embodiment 1 makes is as the positive pole of lithium ion battery, the cycle performance curve that obtains shown in curve A among Fig. 3 shown in.Common lithium acid manganese (lithium manganate having spinel structure) as the cycle performance of anode material for lithium-ion batteries shown in curve B.Can draw, the LiMn2O4 nanometer sheet that the technical program makes 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, nanometer lamella LiMn2O4 structure can provide than short lithium ion transmission channel and bigger specific area, thereby improve the diffusivity of lithium ion in material, thereby further improved the cycle performance of nanometer lamella lithium manganate material.
Described method for preparing anode material of lithium-ion battery technology is simple, and implementation cost is low, is easy to realize industrialization, and does not have noxious substance, environmental friendliness.
Be understandable that, for the person of ordinary skill of the art, can make other various corresponding changes and distortion by technical conceive according to the present invention, and all these change the protection range that all should belong to claim of the present invention with distortion.
Claims (11)
1. the preparation method of an anode material for lithium-ion batteries comprises step:
By stoichiometric proportion, high price manganese salt, low price manganese salt and oxidant are dissolved in deionized water for stirring mix, obtain mixed liquor;
Described mixed liquor is carried out hydro-thermal reaction to obtain slurries;
Described slurries are carried out filtration washing, drying, obtain δ-MnO
2The nanometer sheet material;
According to stoichiometric proportion with lithium salts and described δ-MnO
2The nanometer sheet material mixes, and obtains mixture;
Described mixture is dropped into the even back drying at room temperature that stirs in the organic solution, obtain powder; And
After in oxidizing atmosphere, described powder being carried out sintering, through washing, dry and grind anode material for lithium-ion batteries.
2. the preparation method of anode material for lithium-ion batteries as claimed in claim 1 is characterized in that, described high price manganese 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 high price manganese 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 a in silver permanganate water and crystal and permanganic acid Xi Shui and the 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 a in hypochlorous acid manganese water and crystal and manganese acetate water and the crystal, described oxidant is potassium chlorate, hydrogen peroxide, ammonium persulfate, Peracetic acid, nitric acid, sulfuric acid, at least a in clorox and the 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 comprise with the method that obtains slurries:
Described mixed liquor is poured in the hydro-thermal jar of polytetrafluoroethylene preparation, put into explosion-proof baking oven after sealing described hydro-thermal jar with stainless steel tube, programming rate with 1-20 ℃/min is heated to 100 ℃-160 ℃, is incubated 2-5 days, and then the cooldown rate with 1-20 ℃/min is cooled to room temperature.
5. the preparation method of anode material for lithium-ion batteries as claimed in claim 1 is characterized in that, described lithium salts is at least a in lithium carbonate, lithium acetate, lithium hydroxide, lithium nitrate, lithium oxalate, ethylenediamine tetra-acetic acid lithium salts and the carbamyl phosphate dilithium salt.
6. the preparation method of anode material for lithium-ion batteries as claimed in claim 1 is characterized in that, the method for in the oxidizing atmosphere described powder being handled comprises:
Described powder is placed vacuum tube furnace, and the programming rate with 2-8 ℃ of min-1 in oxidizing atmosphere is heated to 400-800 ℃, keeps after 10-30 hour, and gained powder, then dry 1-100 hour are washed with the deionized water multiple times of filtration in the cold back of stove.
7. the preparation method of anode material for lithium-ion batteries as claimed in claim 6 is characterized in that, described oxidizing atmosphere is at least a in bubbling air atmosphere or the oxygen atmosphere in vacuum tube furnace.
8. the preparation method of anode material for lithium-ion batteries as claimed in claim 1 is characterized in that, described organic solution is at least a in acetone, ethanol, methyl alcohol, chlorination ethanol, dichloroethanes, butanols, dimethylbenzene, amyl acetate and the isopropylbenzene.
9. the preparation method of lithium ion anode material as claimed in claim 1, it is characterized in that, after in described mixture input organic solution, evenly stirring the back drying at room temperature, also repeated multiple times ground is fed into dried mixture and evenly stirs the back drying at room temperature in the organic solution, to obtain powder.
10. anode material for lithium-ion batteries, it is made of the LiMn2O4 nanometer sheet, and the thickness of described LiMn2O4 nanometer sheet is 10nm-50nm, and length and the width of described LiMn2O4 nanometer sheet reach 200nm-500nm.
11. an anode material for lithium-ion batteries, it is made by the preparation method as each described anode material for lithium-ion batteries of claim 1 to 9.
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| CN103641174A (en) * | 2013-12-10 | 2014-03-19 | 中国科学院宁波材料技术与工程研究所 | Nano sheet MnO2-graphene composite material, preparation method thereof and super capacitor |
| 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 |
| CN107915260A (en) * | 2017-11-30 | 2018-04-17 | 中国科学院大连化学物理研究所 | A kind of nanometer MnO of high entropy of transition2The preparation method of particle |
| 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 nanometer MnO of high entropy of transition2The preparation method of particle |
| CN109037613A (en) * | 2018-07-04 | 2018-12-18 | 上海电气集团股份有限公司 | Ruthenic oxide coating spinelle richness lithium LiMn2O4 and preparation method thereof |
| 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 |
| CN113839029A (en) * | 2020-06-24 | 2021-12-24 | 深圳市比亚迪锂电池有限公司 | Lithium-manganese battery |
| 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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