CN105226276A - The preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material - Google Patents
The preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material Download PDFInfo
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- CN105226276A CN105226276A CN201510428437.XA CN201510428437A CN105226276A CN 105226276 A CN105226276 A CN 105226276A CN 201510428437 A CN201510428437 A CN 201510428437A CN 105226276 A CN105226276 A CN 105226276A
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- 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
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses the preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material, metallizing thing after graphite oxide ultrasonic disperse is fully uniformly mixed, through reduction, obtained metal nanoparticle/graphene composite material after dry, and same for composite material source of iron, phosphorus source, lithium source are fully mixed obtained composite precursor, then calcining can obtain.The invention solves Graphene and cause the phenomenon of coated LiFePO 4 for lithium ion batteries inequality with reuniting in LiFePO4 recombination process; Simultaneously contain a small amount of oxygen-containing functional group through reducing obtained Graphene, this oxygen-containing functional group has storage lithium in high potential interval active, can improve material high power charging-discharging ability; The intervention of metal nanoparticle improves the electron transfer capabilities between Graphene synusia in addition, thus it is low to solve LiFePO 4 material electronic conductivity on the whole, the problem that lithium ion diffusion rate is slow, improves lithium iron phosphate dynamic battery high rate performance and quick charge capability.
Description
Technical field
The present invention relates to a kind of lithium iron phosphate positive material of modification, relate in particular to the preparation method that a kind of coated appendix has metal nanoparticle/grapheme lithium iron phosphate material.
Background technology
LiFePO 4 material has chemically stable, with low cost, environmental friendliness, safety and long-life feature, make it the ideal electrode material becoming power vehicle field, but because its special crystal structure causes, self there is slow lithium ion diffusion coefficient and low electronic conductivity, seriously govern the high rate performance of ferric phosphate lithium cell, affect the fast development of power vehicle industry.
Graphene is that carbon atom is through Sp
2the individual layer atomic arrangement of hydridization composition is cellular two dimensional crystal, passes through Sp between its carbon atom
2hybridized orbit is connected, and only has a carbon atom dimensional thickness.The crystal structure of this uniqueness of Graphene, gives its excellent electricity, mechanics and thermal property.Meanwhile, the surface area that Graphene is large, makes it the characteristic with super capacitor.In order to improve the capacity of ferric phosphate lithium cell and doubly forthright, available Graphene carries out surface coating modification to it.Current domestic existing use Graphene carries out the research (CN101752561A) of modification to LiFePO4, but due to the existence of Van der Waals force between graphene layer, that Graphene is very easily reunited, thus affect the premium properties that Graphene originally has, the agglomeration traits of Graphene how is stoped to be worth going further to solve, this invention will in the process of graphenic surface appendix metal nanoparticle, not only hinder Graphene reunion and also improve the electron transfer of graphene film interlayer, use it for the coated of LiFePO 4 material, the energy density of energy-storage battery and doubly forthright can be improved further.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of metal nanoparticle/Graphene composite lithium iron phosphate material, the lithium battery making it prepare has high capacity characteristics and good high rate performance.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for metal nanoparticle/Graphene composite lithium iron phosphate material, makes according to following steps:
(1) take graphite oxide according to the ratio of 0.1g graphite oxide/50ml distilled water and be placed in distilled water, ultrasonic disperse 1h ~ 1.5h, graphite to be oxidized disperses to add metallic compound more completely, the metallic compound added and graphite oxide mass ratio are (1 ~ 7.5): 2, magnetic agitation makes it to dissolve completely, reducing agent is added subsequently to mixed solution, the mass ratio of reducing agent and graphite oxide is (0.5 ~ 1): 1, during use liquid reducer, addition is 5 ~ 15ml, move into water-bath and be heated to 85 DEG C ~ 98 DEG C stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as 60 DEG C of air dry oven dryings, obtained metal nanoparticle/graphene composite material.
(2) by Li, Fe and P mol ratio (1 ~ 1.05): 1:(1 ~ 1.05) take lithium source, source of iron and phosphorus source, carbon source and metal nanoparticle/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, the material taken is placed in ball grinder, add appropriate amount of deionized water or absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min.
(3) composite precursor in (2) is placed in tube furnace; pass into inert gas; treat that air is drained; be warming up to 750 DEG C of calcining 24h; stop passing into protective gas when cooling to 50 DEG C with the furnace; treat that specimen temperature drops to room temperature and takes out, namely obtain metal nanoparticle/Graphene composite lithium iron phosphate material.
Preferably, the graphite oxide of described step (1) is obtained by graphite oxidation, graphite after oxidation sheet surfaces and edge attached containing a large amount of oxygen-containing functional group (-COOH ,-OH and-C-O-C-etc.), make to have excellent hydrophilic ability, ultrasonic process exists in the laminated structure of≤10 layers afterwards.
Preferably, the metallic compound that described step (1) uses is for providing one or more in silver ion, gold ion or platinum ion compound, wherein used silver compound is silver fluoride or silver nitrate, gold compound is gold chloride, and platinum compounds is chloroplatinic acid, potassium chloroplatinate or platinic sodium chloride.
Preferably, described step (1) use reducing agent for hydrazine hydrate or ascorbic acid or sodium borohydride.
Preferably, in metal nanoparticle/graphene composite material that described step (1) obtains, metal nanoparticle comprises one or more mixed metal particles in silver nano-grain, gold nano grain, Pt nanoparticle, described nano particle must have anti-oxidation characteristics, the burning membrane volume (VOX) generated during oxidation is greater than oxide-film and generates the metal volume (VM) consumed, and namely P-B ratio (P-B is than being VOX/VM) is greater than 1.
Preferably, the method of described step (1), in obtained metal nanoparticle/graphene composite material, appendix has the graphenic surface of metal nanoparticle and edge still containing a little oxy radical, it is active that this oxygen-containing functional group (2V-4V) under high potential has storage lithium, improves the reversible capacity under material high magnification; Be attached to the metal nanoparticle difficult drop-off under ultrasonication on Graphene, in conjunction with firm; Metal nanoparticle/Graphene through ultrasonic disperse process is that 1 ~ 10 synusia Rotating fields exists.
Preferably, the lithium source of described step (2) is lithium carbonate, lithium hydroxide, lithium fluoride or lithium acetate; Described source of iron is ferrous oxalate, ferrous acetate or iron oxide; Described phosphorus source is ammonium hydrogen phosphate or ammonium dihydrogen phosphate; Described carbon source is glucose, and in the preparation method that this invention uses, source of iron and phosphorus source can unite two into one, and use ferric phosphate to replace.
Preferably, the inert gas that described step (3) uses is high pure nitrogen, one or more mists in neon, argon gas.
Beneficial effect of the present invention: metal nanoparticle prepared by the present invention/Graphene composite lithium iron phosphate material, solves Graphene and causes the phenomenon of coated LiFePO 4 for lithium ion batteries inequality with reuniting in LiFePO4 recombination process; Simultaneously contain a small amount of oxygen-containing functional group through reducing obtained Graphene, this oxygen-containing functional group has storage lithium in high potential interval active, can improve material high power charging-discharging ability; The intervention of metal nanoparticle improves the electron transfer capabilities between Graphene synusia in addition.Thus it is low to solve LiFePO 4 material electronic conductivity on the whole, the problem that lithium ion diffusion rate is slow, improves lithium iron phosphate dynamic battery high rate performance and quick charge capability.
Accompanying drawing explanation
Fig. 1 is target product made battery first charge-discharge curve chart described in the embodiment of the present invention 1 and conventional graphite alkene composite lithium iron phosphate materials Example;
Fig. 2 is target product made battery high rate performance curve described in the embodiment of the present invention 1 and conventional graphite alkene composite lithium iron phosphate materials Example.
Embodiment
For the ease of the understanding of content of the present invention, below in conjunction with embodiment, the invention will be further described, and following examples are only a part of embodiment of the present invention.
Embodiment 1
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1h, adds 100mgAgNO after graphite dispersion to be oxidized
3abundant stirring makes it to dissolve, subsequently to adding 10ml hydrazine hydrate in mixed solution, move into water-bath and be heated to 95 DEG C of stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as the dry 48h of 60 DEG C of air dry ovens, cold going obtains silver nano-grain/graphene composite material to room temperature.
2, the ratio being 1:1:1 in Li, Fe and P mol ratio takes lithium titanate, ferrous oxalate and ammonium dihydrogen phosphate, glucose and silver nano-grain/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into N
2for protective gas, rise to 750 DEG C of calcining 24h, cool to 50 DEG C of stoppings with the furnace and pass into protective gas, take out when specimen temperature drops to room temperature, namely obtain silver nano-grain/Graphene composite lithium iron phosphate material.
Embodiment 2
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1h, adds 150mgAgNO after graphite dispersion to be oxidized
3stirring makes it fully to mix with graphite oxide, subsequently to adding 10ml hydrazine hydrate in mixed solution, move into water-bath and be heated to 95 DEG C of stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as the dry 48h of 60 DEG C of air dry ovens, cold going obtains silver nano-grain/graphene composite material to room temperature.
2, the ratio being 1:1:1 in Li, Fe and P mol ratio takes lithium titanate, ferrous oxalate and ammonium dihydrogen phosphate, 0.1 ~ the 15wt% being LiFePO4 theoretical yield by silver nano-grain/Graphene takes silver nano-grain/Graphene, glucose takes by the 1wt% of LiFePO4 theoretical yield, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into N
2or Ar gas is as protective gas, rises to 750 DEG C of calcining 24h, cool to 50 DEG C of stoppings with the furnace and pass into protective gas, take out when specimen temperature drops to room temperature, namely obtain silver nano-grain/Graphene composite lithium iron phosphate material.
Embodiment 3
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1.5h, adds 100mgAgNO after graphite dispersion to be oxidized
3abundant stirring makes it to dissolve completely, subsequently to adding 100mg ascorbic acid in mixed solution, move into water-bath and be heated to 95 DEG C of stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as the dry 48h of 60 DEG C of air dry ovens, silver nano-grain/graphene composite material can be obtained.
2, the ratio being 1.05:1:1.05 in Li, Fe and P mol ratio takes lithium titanate, ferrous oxalate and ammonium dihydrogen phosphate, glucose and silver nano-grain/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into H
2as reducibility gas, rise to 750 DEG C of calcining 24h, stop passing into protective gas when cooling to 50 DEG C with the furnace, take out when specimen temperature drops to room temperature, namely obtain silver nano-grain/Graphene composite lithium iron phosphate material.
Embodiment 4
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1.5h, 150mg platinic sodium chloride is added after graphite dispersion to be oxidized, abundant stirring makes it to dissolve completely, subsequently to adding 10ml hydrazine hydrate in mixed solution, moving into water-bath and being heated to 95 DEG C of stirring reaction 1h, naturally cooling rear alcohol and deionized water repeatedly centrifuge washing, by product as the dry 48h of 60 DEG C of air dry ovens, Pt nanoparticle/graphene composite material can be obtained.
2, the ratio being 1:1:1 in Li, Fe and P mol ratio takes lithium titanate, ferrous oxalate and ammonium dihydrogen phosphate, glucose and Pt nanoparticle/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into N
2as protective gas, rise to 750 DEG C of calcining 24h, stop passing into N when cooling to 50 DEG C with the furnace
2, take out when specimen temperature drops to room temperature, namely obtain Pt nanoparticle/Graphene composite lithium iron phosphate material.
Embodiment 5
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1h, 150mg potassium chloroplatinate is added after graphite dispersion to be oxidized, abundant stirring makes it to dissolve completely, subsequently to adding 100mg ascorbic acid in mixed solution, moving into water-bath and being heated to 95 DEG C of stirring reaction 1h, naturally cooling rear alcohol and deionized water repeatedly centrifuge washing, by product as the dry 48h of 60 DEG C of air dry ovens, silver nano-grain/graphene composite material can be obtained.
2, the ratio being 1.05:1:1.05 in Li, Fe and P mol ratio takes lithium titanate and ferric phosphate, glucose and silver nano-grain/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, taken material is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into N
2as protective gas, rise to 750 DEG C of calcining 24h, stop passing into protective gas when cooling to 50 DEG C with the furnace, take out when specimen temperature drops to room temperature, namely obtain silver nano-grain/Graphene composite lithium iron phosphate material.
Embodiment 6
1, by 100mg graphite oxide as in 50ml distilled water, ultrasonic disperse 1.5h, adds 100mgAgNO after graphite dispersion to be oxidized
3stirring makes it fully to mix with graphite oxide, subsequently to adding 100mg ascorbic acid in mixed solution, move into water-bath and be heated to 95 DEG C of stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as the dry 48h of 60 DEG C of air dry ovens, silver nano-grain/graphene composite material can be obtained.
2, the ratio being 1:1:1 in Li, Fe and P mol ratio takes lithium titanate and ferric phosphate, glucose takes by the 1wt% of LiFePO4 theoretical yield, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain LiFePO 4 material in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min.3, be that 0.05:1 takes silver metal nanoparticles/Graphene and iron phosphate material as in Ball-stirring mill by silver nano-grain/Graphene and LiFePO4 mass ratio, add appropriate distilled water and stir 2h, carry out spraying dry after taking-up and obtain composite precursor, and composite precursor is placed in tube furnace, pass into N
2as protective gas, rise to 750 DEG C of calcining 24h, stop passing into protective gas when cooling to 50 DEG C with the furnace, take out when specimen temperature drops to room temperature, namely obtain silver nano-grain/Graphene composite lithium iron phosphate material.
Conventional graphite alkene composite lithium iron phosphate materials Example:
1, by 100mg graphite oxide as in 50ml distilled water, in mixed solution, 10ml hydrazine hydrate is added after ultrasonic disperse 1h, move into water-bath and be heated to 95 DEG C of stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as the dry 48h of 60 DEG C of air dry ovens, cold going obtains grapheme material to room temperature.
2, the ratio being 1:1:1 in Li, Fe and P mol ratio takes lithium titanate, ferrous oxalate and ammonium dihydrogen phosphate, glucose and Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt%, the material taken is placed in ball grinder, add appropriate absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min, and composite precursor is placed in tube furnace, pass into N
2for protective gas, rise to 750 DEG C of calcining 24h, cool to 50 DEG C of stoppings with the furnace and pass into protective gas, take out when specimen temperature drops to room temperature, Graphene composite lithium iron phosphate material can be obtained.
Above content is only citing made for the present invention and explanation; affiliated those skilled in the art make various amendment to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or surmount this scope as defined in the claims, protection scope of the present invention all should be belonged to.
Claims (8)
1. a preparation method for metal nanoparticle/Graphene composite lithium iron phosphate material, is characterized in that, comprise following making step:
1., graphite oxide is placed in distilled water according to the ratio of 0.1g graphite oxide/50ml distilled water, ultrasonic disperse 1h ~ 1.5h, add metallic compound after graphite dispersion to be oxidized, the metallic compound added and graphite oxide mass ratio are (1 ~ 7.5); Abundant stirring makes it to dissolve completely, reducing agent is added subsequently in mixed solution, the mass ratio of reducing agent and graphite oxide is (0.5 ~ 1): 1, during use liquid reducer, addition is 5 ~ 15ml, move into water-bath and be heated to 85 DEG C ~ 98 DEG C stirring reaction 1h, naturally rear alcohol and deionized water repeatedly centrifuge washing is cooled, by product as dry more than the 24h of 60 DEG C of air dry ovens, obtained metal nanoparticle/graphene composite material;
2. be, (1 ~ 1.05) by Li, Fe and P mol ratio: 1:(1 ~ 1.05) take lithium source, source of iron and phosphorus source, carbon source and metal nanoparticle/Graphene take by the 1wt% of LiFePO4 theoretical yield and 0.1 ~ 15wt% respectively, the material taken is placed in ball grinder, add appropriate amount of deionized water or absolute ethyl alcohol, to obtain composite precursor in the dry 48h of 80 DEG C of drying boxes after the rotating speed ball milling 24h of 500r/min;
3., by step 2. in composite precursor be placed in tube furnace, pass into inert gas, after air is drained; be warming up to 750 DEG C of calcining 24h; stop passing into protective gas when cooling to 50 DEG C with the furnace, treat that specimen temperature drops to room temperature and takes out, namely obtain metal nanoparticle/Graphene composite lithium iron phosphate material.
2. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, it is characterized in that, described step 1. described in graphite oxide be obtained by graphite oxidation, graphite after oxidation sheet surfaces and edge attached containing a large amount of oxygen-containing functional group (-COOH ,-OH and-C-O-C-), ultrasonic process exists in the laminated structure of≤10 layers afterwards.
3. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, it is characterized in that, the metallic compound that 1. described step adds is for providing one or more in silver ion, gold ion or platinum ion compound, wherein used silver compound is silver fluoride or silver nitrate, gold compound is gold chloride, and platinum compounds is chloroplatinic acid, potassium chloroplatinate or platinic sodium chloride.
4. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, is characterized in that, the reducing agent that 1. described step uses is hydrazine hydrate or ascorbic acid or sodium borohydride.
5. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, it is characterized in that, described metal nanoparticle comprises one or more mixed metal particles in silver nano-grain, gold nano grain, Pt nanoparticle.
6. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, is characterized in that, described appendix has the graphenic surface of metal nanoparticle and edge still containing a little oxy radical; Be attached to the metal nanoparticle difficult drop-off under ultrasonication on Graphene, in conjunction with firm; Metal nanoparticle/Graphene through ultrasonic disperse process is that 1 ~ 10 synusia Rotating fields exists.
7. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, is characterized in that, described step lithium source is 2. lithium carbonate, lithium hydroxide, lithium fluoride or lithium acetate; Described source of iron is ferrous oxalate, ferrous acetate or iron oxide; Described phosphorus source is ammonium hydrogen phosphate or ammonium dihydrogen phosphate; Described carbon source is glucose.In this method used, source of iron and phosphorus source can unite two into one, and use ferric phosphate to replace.
8. the preparation method of a kind of metal nanoparticle according to claim 1/Graphene composite lithium iron phosphate material, is characterized in that, described step inert gas is 3. one or more mists in high pure nitrogen, neon, argon gas.
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Cited By (9)
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| CN106058187A (en) * | 2016-07-13 | 2016-10-26 | 张静 | Preparation method of lithium iron phosphate/graphene oxide/platinum composite electrode material |
| CN106744778A (en) * | 2016-12-28 | 2017-05-31 | 湖北金泉新材料有限责任公司 | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material |
| CN106935838A (en) * | 2017-05-05 | 2017-07-07 | 南京理工大学 | The method for preparing the LiFePO4 quaternary composite of unidirectional preferential growth high electrochemical activity |
| CN107195891A (en) * | 2017-06-30 | 2017-09-22 | 绍兴文理学院 | A kind of preparation method of lithium battery graphene composite negative pole |
| CN107195913A (en) * | 2017-05-18 | 2017-09-22 | 北京化工大学 | A kind of LiFePO 4 Supported Pt Nanoparticles oxygen reduction electro-catalyst and preparation method thereof |
| CN107359343A (en) * | 2017-07-28 | 2017-11-17 | 南京理工大学 | The preparation method of one species spiral shape silver nanochains conductor bridging modified phosphate iron lithium composite material |
| CN107994219A (en) * | 2017-11-27 | 2018-05-04 | 桑顿新能源科技有限公司 | A kind of metal-doped composite positive pole of graphene coated and preparation method thereof |
| CN108400310A (en) * | 2018-03-15 | 2018-08-14 | 湖南烯能新材料有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
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