CN102195031A - Method for preparing nano-wire silicon carbide/graphite composite cathode materials of lithium-ion batteries at high temperature - Google Patents
Method for preparing nano-wire silicon carbide/graphite composite cathode materials of lithium-ion batteries at high temperature Download PDFInfo
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Abstract
The invention provides a method for preparing nano-wire silicon carbide/graphite composite cathode materials of lithium-ion batteries at high temperature. The method is characterized by comprising the steps of: (1) hydrolyzing starch so as to obtain glucose; (2) preparing a mixed sol with the glucose and silica sol; (3) drying the mixed sol; (4) performing a gelation treatment to the mixed sol; (5) placing the obtained gel in a crucible, putting the crucible in an atmosphere reaction furnace, and pumping vacuum; (6) introducing argon into the atmosphere reaction furnace; (7) sintering the gel in the inert atmosphere; (8) cooling to a room temperature, thus obtaining a mixture of nano-wire silicon carbide and graphite.
Description
Technical field
The present invention relates to the method that a kind of high temperature prepares lithium ion cell nano line carborundum/composite cathode material of silicon/carbon/graphite, relate to a kind of preparation method of nano-line silicone carbide/composite cathode material of silicon/carbon/graphite of the lithium ion battery negative with height ratio capacity, stable cycle performance in other words.Belong to the lithium ion battery field.
Background technology
The whole world because the earth atmosphere that combustion of fossil fuels causes pollution is serious day by day, day by day aggravates global greenhouse effect over 100 years.Global in recent years temperature obviously raises, and melt in the glacier, and raise on the sea level.Urban atmospheric pollution more than 60% owing to due to the burning petrol and diesel oil tail gas,, contain the harmful chemical component that causes lung cancer in the tail gas of automobile burning generation according to foreign study.In addition, in year surplus the exploitation of oil only can keep 100, energy shortage has appearred in a lot of countries, and the exploitation regenerative resource is day by day urgent.The vehicles such as development electric automobile are useful, and lithium ion battery shows bright development prospect as the energy storage instrument.The energy-storage battery technology belongs to the underlying issue that will solve in the electric automobile field.The trend of quickening appears in the negative material of lithium rechargeable battery, to satisfy practical needs.The used negative material of secondary lithium battery is a graphite crystallization raw material of wood-charcoal material.Lithium ion battery carbon material negative pole is present commercial product.The advantage of this material is that cycle period is long, and cost is low.But current potential is lower than lithium, easily at the surface deposition Li dendrite, has the lithium ion battery potential safety hazard; The raw material of wood-charcoal material is as the theoretical capacity 372mAh/g of lithium ion battery.Usually, in fact the capacity of carbon cathode material product can only reach 330mAh/g.The higher negative materials of high power density application need capacity such as electric automobile.This has limited the further application of carbon cathode material.The raw material of wood-charcoal material can improve through its capacity after the graphitization, but complex process, cost is higher, unstable properties.In view of this, the exploitation of various non-carbon cathode materials is very active.Silica-base material is arranged, and as silicon grain, silicon dioxide etc., the capacity of these negative materials is higher.Behind the process circulation experiment, its cycle life remains to be improved, and has potential safety hazard.Such as, the theoretical capacity of silicon can reach 4200mAh/g, U.S. Si Tanfo university has synthesized large-area nano linear carbon array on iron plate, adopt general electrolyte, its experiment as lithium ion battery negative shows, first capacity also can reach peak capacity 75% in addition higher, can keep this capacity almost constant in the cycle period of test.But behind long cycle period, big (the CANDACE K.CHAN et al.Nature.Published online:16December 2007 of its capacity attenuation; Doi:10.1038/nnano.2007.411), there is further improved huge space in this explanation silicon nanowire as the use of ion cathode material lithium, and its prospect is very tempting; There is same phenomenon in silicon dioxide.Next is the alloy-based material, and as alusil alloy, mg-si master alloy etc. have higher capacity, yet its cycle life is undesirable equally.But capacity and cycle life than silicon materials have no small improvement.In recent years, because the rise of nano material, researcher's attentiveness of lithium ion battery negative material concentrated on field of nanometer material technology.From big class, present hot of research and development, one side concentrates on graphitization, the nanometer of raw material of wood-charcoal material, such as making the raw material of wood-charcoal material through the graphite crystallization, cycle performance is improved; Nanometer can be created higher specific surface and space, lithium ion is stored strengthen the raising capacity.Its processing technology complexity causes cost to rise.Want to reach low-cost, high reliability also needs further research.On the other hand, the nano material of kamash alloy progress is very fast, tin oxide for example, and theoretical capacity is 3300mAh/g, its capacity first as lithium ion battery negative material reaches 3000mAh/g.Its cycle life requires further improvement, so that can be used for energy storage industry.Equally, the capacity of thin film based magnesium base alloy can reach very high.Pure carborundum is water white crystal.Industry carborundum is different with content because of the kind of impurities, and is pale yellow, green, indigo plant and even black, and transparency is different and different with its purity.The silicon carbide whisker body structure is divided into six sides or rhombohedral α-SiC and cubical β-SiC (title cubic silicon carbide).α-SiC constitutes many different variants owing to the stacking sequence of carbon in its crystal structure and silicon atom is different, found 70 surplus kind.β-SiC changes α-SiC in time more than 2100 ℃.Carborundum claims corundum or fire sand again.Molecular formula is SiC, and its hardness is between corundum and diamond, and mechanical strength is higher than corundum, can be used as abrasive material and some other industrial materials use.A kind of method now is provided, prepares nanometer silicon carbide, its as lithium ion battery negative first capacity can reach 1210mAh/g.Industrial carborundum was succeeded in developing in 1891, was manufactured abrasive the earliest.Though there is small amount of carbonized silicon to exist in the aerolite and the earth's crust, not finding as yet so far can be for the mineral resources of exploitation.
Carborundum is because stable chemical performance, conductive coefficient height, thermal coefficient of expansion is little, anti-wear performance good, except that do abrasive material with, also have a lot of other purposes, carborundum also is used to make the electric heating element Elema in a large number.
The carborundum technical indicator has, and maximum service temperature reaches more than 1450 ℃, strength at normal temperature 45Mpa, and 1400 ℃ of high temperature break resistant intensities are 50Mpa, and 1000 ℃ of coefficient of thermal expansions are 0.42-0.48%, and conductive coefficient is 16.3-16.7w/m.k in the time of 350 ℃.
Carborundum has advantages such as lightweight, high temperature resistant, wear-resisting, high elastic modulus and anti-severe rugged environment, and it is widely used in fields such as structural ceramics, ceramic on metal and engineering plastics.Forefathers are for a long time to studies show that of silicon carbide body material, migration is closed to carborundum for lithium ion.This may be that chemical bond is stronger because of carborundum hardness height, and the coefficient of expansion is low, is difficult to form silicon lithium and carbon lithium fit structure in crystal, intercepts the lithium ion migration.But this is the judgement under the prerequisite of silicon carbide body material, has ignored these situations of amorphous state carbonization silicon or nanometer silicon carbide.At nanoscale, the carborundum crystals material has certain elastoplasticity, and surface area increases, and the chance that surface silicon atoms and carbon atom and lithium ion form complex increases, and this provides the possibility of storage lithium.People such as P.N.Kumta (Journal of Power Sources Volume 130, Issues 1-2,2004,275-280) adopt ball grinding technique to obtain the silicon carbide composite of amorphous charcoal and about 10nm diameter, this Si-SiC nano-complex as the lithium ion battery negative material capacity is～370mAh/g.This experiment is not judged the capacity of the sort of material.Because the capacity of amorphous silicon can reach 4000mAh/g, capacity attenuation is very big, so according to supposition, this may be the capacity of nanometer silicon carbide.Yet because the existence of amorphous silicon, the convincingness that makes nanometer silicon carbide become this capacity has reduced.Mention porous Si/C compound among the patent USPTO Application #:20090029256 as negative material, clear and definite this material heats up and can constitute the SiC interface of lithium ion passivation; And mentioned Si among the US20090291371, and C, the negative material of three kinds of atomic buildings of O wherein contains the Si-C key, but carborundum (silicon carbide) thing phase do not occur, and indexs such as the capacity of the material that this has silicon-carbon bonds and cycle-index are not described yet.These phenomenons show that nanometer silicon carbide should have certain lithium storage content, but this capacity is subjected to multiple effects limit.
Summary of the invention
The objective of the invention is to propose a kind of novel lithium ion battery negative material, this material is a nano-line silicone carbide, it is on the low side to be intended to solve lithium ion battery negative raw material of wood-charcoal material capacity, the short and body material carborundum of other alloy-based negative material cycle life is to the problem of lithium ion closure, thereby the carbofrax material that is used for the lithium ion battery negative pole and the preparation method of a kind of height ratio capacity, stable cycle performance are provided.At carborundum (English silicon carbide, chemical formula SiC) problem of body material passivation of lithium ion migration, prepare uniform nanometer silicon carbide with sintering technology, the high strength of based on silicon carbide, the characteristics that anti-severe rugged environment is stable, thereby the energy density and the power characteristic of raising lithium ion battery negative material.Can observe in nano-line silicone carbide/graphite composite material, nano-line silicone carbide length reaches millimeter level, and diameter wherein also comprises nanotube carborundum in 10～500nm scope, present form of spherical particles be graphite or.The preparation of nano-line silicone carbide/composite cathode material of silicon/carbon/graphite, can realize by following technology: (one) is 1 according to the mol ratio of silicon and carbon: the ratio of (0.5～3) takes by weighing a certain amount of starch and Ludox respectively; (2) be the starch that takes by weighing 1 according to volume ratio with deionized water: (10～20) obtain solution, stir on the mechanical agitation instrument under the room temperature; Dropping＜10ml concentration is 10% sulfuric acid solution in this starch solution, makes the starch hydrolysis, and stirs on magnetic stirring apparatus and be heated to 45～60 ℃, and drying obtains powder, and this is a glucose; (3) the Ludox preparation mixed sols that takes by weighing in glucose powdery thing that obtains in the step (two) and the step (), stir the colloidal sol that forms homogeneous transparent with mechanical agitator; (4) under 80～100 ℃ temperature conditions, colloidal sol is carried out gelation and handle, obtain white gels; (5) gel that obtains is placed in the crucible, the crucible that fills gel is placed in the atmosphere reacting furnace, take out system vacuum, make the vacuum degree 10 of atmosphere reacting furnace
-3Pa～0.2Pa; (6) in the vacuum reaction stove, feed argon gas, make furnace gas pressure remain on 0.05～2MPa scope; (7) with the programming rate heating atmosphere reacting furnace of 15～25 ℃/min, 1350～1650 ℃ sintering temperatures 0.5～3 hour; (8) continue to keep argon gas atmosphere, stop heating, naturally cool to room temperature, promptly obtain nano-line silicone carbide and graphite mixture.Salient point appears in the nano-line silicone carbide surface, and branch is arranged, two ends diameter difference.
Compare with existing the whole bag of tricks, characteristics of the present invention are:
(1) be raw material with starch, its wide material sources.
(2) starch hydrolysis process does not need thorough hydrolysis to glucose.
(3) used sulfuric acid is recyclable uses again.
(4) in hydrolytic process not with an organic solvent, do not produce pernicious gas.
(5) the gel sintering can the uniform carborundum of production size.
(6) product has only carborundum and graphite in mutually.
Description of drawings
Fig. 1 is 1000 times of electron microscope scanning figure that are hydrolyzed to nano-line silicone carbide/graphite composite material that the gel sintering process of glucose and Ludox preparation obtains by starch; Fig. 2 is nano-line silicone carbide/graphite composite material x-ray diffraction spectra; Fig. 3 is to be the voltage curve that impulse electricity experiment is carried out in active material assembled battery with nano-line silicone carbide/graphite.
Embodiment
The present invention is with the formal specification of Comparative Examples and embodiment method provided by the present invention.
Comparative Examples 1 of the present invention, be that commercially available granularity is made slurry by 70: 20: 10 mass ratio less than carborundum and acetylene black, the Kynoar (PVDF) of 5um in N-methyl pyrrolidone (NMP) medium, coat and carry out drying on the Copper Foil, make electrode film thus.With metallic lithium foil is to electrode, U.S. CE LGARD company polypropylene screen is a barrier film, 1MLiPF6/ (PC+DMC) (1: 1) electrolyte, under the current density of 0.1mA/cm2,0.02-0.05V voltage range in discharge and recharge experiment, embedding the lithium capacity first is 12mAh/g, and taking off the lithium capacity is 9mAh/g, and coulombic efficiency is 75%.The 20th time embedding lithium capacity is 7mAh/g, and taking off the lithium capacity is 4mAh/g, through 20 circulation volumes, 44% (with respect to taking off the lithium capacity first) of having decayed.Explanation is that the electrode embedding lithium capacity of active material is very low with micron particles shape carborundum, and decay is fast.
Embodiment 1 present embodiment is realized a kind of nano-line silicone carbide of preparation by following steps: (one) takes by weighing 21 gram starch, and hydrolysis obtains glucose, and is standby; (2) take by weighing 14 gram Ludox, add deionized water and mix, make colloidal sol with glucose in (one); (3) in vacuum drying chamber in 90 ℃ of dry gained colloidal sols 12 hours, make gel; (4) gel that obtains is placed in the crucible, the crucible that fills gel is placed in the atmosphere reacting furnace, take out system vacuum, make the vacuum degree 10 of atmosphere reacting furnace
-2Pa; (5) in the vacuum reaction stove, feed argon gas, make furnace gas pressure remain on 0.1MPa; (6) with the programming rate heating atmosphere reacting furnace of 20 ℃/min, 1510 ℃ sintering temperatures 2 hours; (7) continue to keep argon gas atmosphere, stop heating, naturally cool to room temperature, promptly obtain nano-line silicone carbide and (or) mixture of graphite.The synthetic nano-line silicone carbide of present embodiment is made up of silicon and carbon, and it is made up of 43～69% carbon and 31～57% silicon according to mass percent, and it is made up of the nano-line silicone carbide of 0～30% graphite and 70～100% to press the solid phase mass percent.Salient point appears in the nano-line silicone carbide surface, and branch is arranged, two ends diameter difference, as shown in Figure 1.
Adopt Comparative Examples 1 described method to prepare electrode the nano-line silicone carbide/graphite composite material of the inventive method preparation, its battery assembly method and test condition are all with Comparative Examples 1.Embedding lithium capacity is 859mAh/g first, and taking off lithium lithium capacity is 859mAh/g, and coulombic efficiency is 100%.The 20th time embedding lithium capacity is 859mAh/g, and taking off the lithium capacity is 859mAh/g, through 20 circulation volumes, 0% (with respect to taking off the lithium capacity first) of having decayed.Explanation is that the electrode embedding lithium capacity of active material is higher with nano-line silicone carbide/graphitic carbon composite material, and decay hardly.As seen the cyclical stability of nano-line silicone carbide/graphite composite material be improved significantly.If in Comparative Examples 1, keep other condition constant, strengthen the voltage tester scope to 4.2V, then 2445mAh/g is taken in the capacity suction one of the nanocrystalline carborundum/amorphous state carbonization silicon/composite cathode material of silicon/carbon/graphite of the inventive method preparation to.As shown in Figure 2, the x ray spectrum of the nano-line silicone carbide/graphite composite material of the present invention's preparation, (carborundum scattering peak combination herein shows that carborundum belongs to cubic structure except that the carborundum scattering, be the many types of carborundum of β), do not find the scattering peak of other material, illustrate that this sintering process only produces nano-line silicone carbide.But other sintered product thing contains two kinds of things of carborundum and graphite mutually mutually.Because the embedding lithium theoretical capacity of graphite has only 372mAh/g, can infer that the embedding lithium capacity of the 859mAh/g of actual measurement is produced by nano-line silicone carbide.This illustrates that also the nano-line silicone carbide key is open to lithium.Its reason has two, the one, the nano-line silicone carbide bond energy descends, lithium ion embeds becomes possibility, next is that nano-line silicone carbide has bigger modulus of elasticity, nano-line silicone carbide distortion behind the embedding lithium, but embedding lithium and to take off in the lithium process nano-line silicone carbide volumetric expansion less, this just causes embedding lithium capacity height.And because silicon carbide structure is stable, the also corresponding raising of reversible capacity, capability retention is almost constant, and its cycle-index of anti-severe rugged environment can be very high.This explanation has only nanometer silicon carbide to the lithium ion high storage capacity is contributive.
The dissimilarity of embodiment 2 present embodiments and embodiment 1 is to get in the step () starch 30 grams, with Ludox preparation colloidal sol mixed liquor.Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 3 present embodiments and embodiment 1 is that the vacuumize temperature of colloidal sol mixed liquor in the step (three) is 100 ℃.Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 4 present embodiments and embodiment 1 is to make furnace gas pressure reach 0.07MPa in the step (five).Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 5 present embodiments and embodiment 1 is to make furnace gas pressure reach 1.2MPa in the step (five).Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 6 present embodiments and embodiment 1 is that sintering time is 3 hours in the step (six).Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 7 present embodiments and embodiment 1 is to carry out in the step (six) sintering under 1550 ℃ temperature.Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 8 present embodiments and embodiment 1 is to carry out in the step (six) sintering under 1600 ℃ temperature.Other step is identical with specific embodiment 1.
The dissimilarity of embodiment 9 present embodiments and embodiment 1 is in the step (seven) cool to room temperature in cooling water recirculation system.Other step is identical with specific embodiment 1.
List of references
1. Guo is to cloud, Hao Yajuan.The sol-gel process of SiC nano fiber is synthetic.Functional material, 2004 (35), supplementary issue, p2855-2857.
2. Chen Jing.A kind of synthetic method of silicon carbide nanometer line.The Huaiyingong College journal, the 15th the 3rd phase of volume, 2006, p50-52.
Claims (10)
1. lithium ion battery carbonization silicon/graphite or carbon compound cathode materials is characterized in that this composite negative pole material is made up of nano-line silicone carbide and graphite granule.
2. by the described a kind of lithium ion cell nano line carborundum/composite cathode material of silicon/carbon/graphite of claim 1, it is characterized in that the nano-line silicone carbide content range is 50-100wt% in this composite negative pole material, the content of graphite scope is 0-50wt%.
3. press the preparation method of the described a kind of lithium ion cell nano line carborundum/composite cathode material of silicon/carbon/graphite of claim 2, it is characterized in that the preparation of lithium ion cell nano line carborundum/composite cathode material of silicon/carbon/graphite, can realize by following technology: (one) is 2 according to the mol ratio of silicon and carbon: the ratio of (1～6) takes by weighing a certain amount of starch and Ludox respectively; (2) be the starch that takes by weighing 1 according to volume ratio with deionized water: (10～20) obtain solution, stir on the mechanical agitation instrument under the room temperature; Dropping＜4ml concentration is 10% sulfuric acid solution in this starch solution, makes the starch hydrolysis, and stirs on magnetic stirring apparatus and be heated to 45～60 ℃, and drying obtains glucose powdery thing; (3) the Ludox preparation mixed sols that takes by weighing in glucose powdery thing that obtains in the step (two) and the step (), stir the colloidal sol that forms homogeneous transparent with mechanical agitator; (4) under 80～100 ℃ temperature conditions, colloidal sol is carried out gelation and handle, obtain white gels; (5) gel that obtains is placed in the crucible, the crucible that fills gel is placed in the atmosphere reacting furnace, take out system vacuum, make the vacuum degree 10 of atmosphere reacting furnace
-3Pa～0.2Pa; (6) in the vacuum reaction stove, feed argon gas, make furnace gas pressure remain on 0.05～2Pa scope; (7) with the programming rate heating atmosphere reacting furnace of 15～25 ℃/min, 1350～1750 ℃ sintering temperatures 0.5～3 hour; (8) continue to keep argon gas atmosphere, stop heating, naturally cool to room temperature, promptly obtain the mixture of nano-line silicone carbide and graphite.
4. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology, it is characterized in that in the step () that mol ratio according to silicon and carbon is that 2: 5 ratio takes by weighing respectively in a certain amount of starch and Ludox and the step (two) starch solution is dripped 10% dilution heat of sulfuric acid, make the starch hydrolysis, stirring also is heated to 45～60 ℃, obtains powder.
5. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that the Ludox that takes by weighing in middle powder that obtains of step (three) and the step () is mixed with mixed sols.
6. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that under 95 ℃ of temperature conditions mixed sols being carried out gelation in the step (four) handles.
7. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that making furnace gas pressure reach 0.8Pa in the step (six).
8. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that the atmosphere sintering time is 1 hour in the step (seven).
9. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that sintering remains on 1520 ℃ in the step (seven).
10. a kind of lithium ion cell nano line carborundum according to claim 3/composite cathode material of silicon/carbon/graphite preparation technology is characterized in that recirculated water cooling in the step (eight).
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Cited By (9)
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| CN102646812A (en) * | 2012-04-24 | 2012-08-22 | 东华大学 | Structure of cathode material of lithium ion battery |
| CN103151563A (en) * | 2012-06-27 | 2013-06-12 | 深圳市海太阳实业有限公司 | Polymer cell and preparation method thereof |
| CN105355819A (en) * | 2015-10-13 | 2016-02-24 | 深圳宏泰电池科技有限公司 | Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof |
| CN107001052A (en) * | 2014-11-18 | 2017-08-01 | 帕德博恩大学 | Method for producing the electrode material for battery electrode |
| CN108666543A (en) * | 2018-04-17 | 2018-10-16 | 同济大学 | A kind of spongy C-SiC composite material and preparation methods in sea |
| CN110194665A (en) * | 2019-07-18 | 2019-09-03 | 平顶山市信瑞达石墨制造有限公司 | A kind of graphite cooker and its preparation process |
| CN112777591A (en) * | 2021-01-15 | 2021-05-11 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| CN112838200A (en) * | 2021-02-02 | 2021-05-25 | 衡阳市瑞启新能源有限公司 | Semiconductor lithium ion storage battery cathode and preparation method thereof |
| CN116014113A (en) * | 2023-03-23 | 2023-04-25 | 宁德新能源科技有限公司 | Negative electrode material, secondary battery, and electronic device |
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| CN102646812A (en) * | 2012-04-24 | 2012-08-22 | 东华大学 | Structure of cathode material of lithium ion battery |
| CN103151563A (en) * | 2012-06-27 | 2013-06-12 | 深圳市海太阳实业有限公司 | Polymer cell and preparation method thereof |
| US11165056B2 (en) * | 2014-11-18 | 2021-11-02 | Universität Paderborn | Method of producing an electrode material for a battery electrode |
| CN107001052A (en) * | 2014-11-18 | 2017-08-01 | 帕德博恩大学 | Method for producing the electrode material for battery electrode |
| US20170338481A1 (en) * | 2014-11-18 | 2017-11-23 | Universität Paderborn | Method of Producing an Electrode Material for a Battery Electrode |
| CN107001052B (en) * | 2014-11-18 | 2020-12-01 | 帕德博恩大学 | Method for producing electrode material for battery electrode |
| CN105355819A (en) * | 2015-10-13 | 2016-02-24 | 深圳宏泰电池科技有限公司 | Lithium-rich manganese-based high-energy-density lithium-ion battery and preparation method thereof |
| CN108666543A (en) * | 2018-04-17 | 2018-10-16 | 同济大学 | A kind of spongy C-SiC composite material and preparation methods in sea |
| CN110194665A (en) * | 2019-07-18 | 2019-09-03 | 平顶山市信瑞达石墨制造有限公司 | A kind of graphite cooker and its preparation process |
| CN112777591A (en) * | 2021-01-15 | 2021-05-11 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| CN112777591B (en) * | 2021-01-15 | 2022-02-22 | 无锡东恒新能源科技有限公司 | Preparation method of lithium battery negative electrode material |
| CN112838200A (en) * | 2021-02-02 | 2021-05-25 | 衡阳市瑞启新能源有限公司 | Semiconductor lithium ion storage battery cathode and preparation method thereof |
| CN116014113A (en) * | 2023-03-23 | 2023-04-25 | 宁德新能源科技有限公司 | Negative electrode material, secondary battery, and electronic device |
| CN116014113B (en) * | 2023-03-23 | 2023-09-19 | 宁德新能源科技有限公司 | Negative electrode material, secondary battery, and electronic device |
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Application publication date: 20110921 |