CN102881870A - Lithium ion battery silicon substrate lithium salt composite negative electrode material and preparation method and application thereof - Google Patents
Lithium ion battery silicon substrate lithium salt composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium ion battery silicon substrate lithium salt composite negative electrode material and a preparation method and application thereof. The method includes that silicon monoxide and lithium salt are mixed and ground uniformly according to a mass ratio of 1.2-2.4:1, are transferred into a tubular furnace and react in an inert gas atmosphere under the temperature of 500-800 DEG C for 6-24 hours, and a reaction product, a graphite carbon material and zirconia balls are mixed according to a mass ratio of 1:(0.5-1):(15-20) and are mechanically milled at a rotational speed of 200-400 rotations/ minute for 8-30 hours to obtain the lithium ion battery silicon substrate lithium salt composite negative electrode material. The preparation method is simple in processing, convenient in implementation and cheap in raw materials, and when applied to a lithium ion battery as a negative electrode material, the lithium ion battery silicon substrate lithium salt composite negative electrode material has the advantages of fine electrochemical performance, high specific capacity and fine cycle performance.
Description
Technical field
The invention belongs to the lithium ion battery negative material preparation field, particularly silica-based lithium salts composite negative pole material of a kind of lithium ion battery and preparation method thereof and application.
Background technology
Along with the development of modern living standard and science and technology, people are increasing to consumption and the demand of the energy.In the face of day by day exhausted traditional energy, seeking a kind of reproducible novel energy becomes people's exigence.In numerous regenerative resources, to have a specific energy large because of it for lithium ion battery, has extended cycle life, and security performance is good, and is nuisanceless etc., and advantage becomes a kind of ideal selection.Electrode material is the key factor that determines performance of lithium ion battery, and business-like carbon negative pole material is near its theoretical capacity (372mAhg in the market
-1), be difficult to have again room for promotion.Researcher is devoted to seek a kind of non-carbon negative pole material of alternative material with carbon element always in recent years, and main research comprises nitride, silica-base material, tin-based material and other alloy materials etc.Wherein silicon can form Li with lithium as negative material
12Si
7, Li
13Si
4, Li
7Si
13And Li
22Si
4Up to 4200mAh/g, thereby become the focus of people's research Deng, theoretical capacity.But the doff lithium mechanism of present silicon based anode material is that silicon and lithium generation chemical reaction generate Li
xThe Si compound forms 7 kinds of Li altogether according to different lithium-inserting amounts
xSi compound, and each Different L i
xThe Si compound has different crystal structures.Therefore the removal lithium embedded that is accompanied by in the charge and discharge process will be the variation of different-alloy compound, and these changes are very easy to cause the variation of material structure, cause the pole piece efflorescence to be lost efficacy; And, although silicon based anode material has very high specific capacity, in the doff lithium process, show huge Volumetric expansion (300%), so that efficient and stable circulation performance are all relatively poor first.
For the problems referred to above, application number is 200810048240.3, name is called: " preparation method of sphericity lithium ion battery silicon/stannum binary lithium-storing precursor composite cathode material " discloses a solution, this invention is by reacting reducing agent (graphite), lithium metal, silica and tin oxide mixed grinding under inert gas, wherein, reducing agent reduces active material pure silicon and the pure tin that obtains Nano grade to silica and tin oxide, and lithium metal has then generated Li
4SiO
4Compound, the nano-silicon of generation, tin particles are dispersed in the buffering matrix with lithium-containing compound.Although this invention can solve the problems such as Volumetric expansion to a certain extent, but many shortcomings have also appearred in this invention: (1) introduces lithium metal must be at sintering under the inert atmosphere conditions, and abnormally dangerous, lithium metal is easy to blast on fire, is not suitable for large-scale production; (2) silica and tin oxide are difficult to thoroughly reduction, because the reducing condition of different oxides is different (such as temperature etc.); (3) all still pure nano pure silicone, tin of the final active material overwhelming majority, simple metal still has very large Volumetric expansion; (4) the active material pure silicon of 10nm size and pure tin are very easy to reunite, and are difficult to carry out dispersion treatment, and the metal after the reunion and inhibition volumetric expansion useless have increased the difficulty that pole piece is made on the contrary.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide the preparation method of the silica-based lithium salts composite negative pole material of a kind of lithium ion battery.
A further object of the present invention is to provide the lithium ion battery that is obtained by above-mentioned preparation method silica-based lithium salts composite negative pole material.
Another object of the present invention is to provide the application of the silica-based lithium salts composite negative pole material of above-mentioned lithium ion battery.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of the silica-based lithium salts composite negative pole material of a kind of lithium ion battery comprises following concrete preparation process:
(1) be that the ratio of 1.2～2.4:1 is mixed and ground and evenly obtains mixture in mass ratio with silicon monoxide, lithium salts;
(2) mixture that step (1) is made places reactor, passes into inert gas and is warming up to 500 ℃～800 ℃ afterreaction 6～24h in reactor, obtains product;
(3) product that step (2) is made and graphite-like material with carbon element are 1:(0.5～1 in mass ratio) ratio mix, the gained mixture is mechanical ball milling 8～30h under 200～400rpm/min rotating speed, obtains the silica-based lithium salts composite negative pole material of lithium ion battery;
Wherein,
In the step (1), described silicon monoxide is 200～325 order granular sizes;
In the step (1), described lithium salts is 500 ℃～800 ℃ lower decomposable lithium salts, is preferably a kind of in lithium hydroxide, lithium carbonate or the lithium nitrate;
In the step (2), described inert gas is 500 ℃～800 ℃ lower inactive gases, is preferably a kind of in nitrogen that purity is purity 99.999% or the argon gas;
In the step (2), the speed that described intensification is preferably with 2～5 ℃/min heats up;
In the step (3), the mixture of described product and graphite-like material with carbon element is the preferred zirconia ball that adds before ball milling, and wherein, the ratio of grinding media to material of zirconia ball and mixture is 10～15:1 proportioning in mass ratio;
In the step (3), described graphite-like material with carbon element is a kind of in native graphite, electrographite or the modified graphite;
The silica-based lithium salts composite negative pole material of a kind of lithium ion battery is prepared by above-mentioned preparation method.
The application of the silica-based lithium salts composite negative pole material of described lithium ion battery in the preparation anode plate for lithium ionic cell, comprise following concrete steps: with the silica-based lithium salts composite negative pole material of described lithium ion battery and binding agent, conductive agent in mass ratio (75～85): (15～5): 10 evenly mix, be coated on the Copper Foil behind the furnishing slurry, and through vacuumize 5～24 hours, roll-in, obtain anode plate for lithium ionic cell;
Wherein,
It is the 80:10:10 proportioning in mass ratio preferably that the silica-based lithium salts composite negative pole material of described lithium ion battery and binding agent, conductive agent are pressed;
Described binding agent is a kind of in binding agent LA132 or the polyvinylidene fluoride (PVDF);
Described conductive agent is a kind of in conductive black or the nano-sized carbon;
The thickness of described coating is 100～180 microns;
The thickness of described roll-in is 75～150 microns;
Described vacuum drying temperature is 50 ℃～110 ℃.
The present invention adopts lithium salts and silicon monoxide to carry out obtaining with the graphite material grinding after the solid phase reaction.Wherein, lithium salts and silicon monoxide carry out obtaining comprising the product of silicon, lithium metasilicate or lithium metasilicate after the reaction in the solid phase reaction in addition, because the silicon monoxide that adds is excessive, therefore, also have part and unreacted silicon monoxide in the product.
Active material of the present invention mainly is silicon monoxide and silicon, contains simultaneously constitutionally stable lithium metasilicate or lithium metasilicate as the buffering matrix.Silicon monoxide has excellent chemical property as cell negative electrode material, introduces the bulk effect that oxygen (silicon monoxide) can effectively be alleviated silicon in silicon, can form Li in the process of embedding lithium first
2O along with the variation of lithium-inserting amount, although irreversible capacity loss increases first, has also played the effect of certain alleviation volumetric expansion simultaneously, relative pure silicon, and what structure will be stable is many, therefore, the cyclical stability of battery is significantly promoted.In addition, lithium metasilicate among the present invention or lithium metasilicate all have more stable structure, take off in the lithium ion embedding and to be difficult for recurring structure distortion in the process, as alleviating the Volumetric expansion matrix, therefore have good stable circulation performance, circulate, mean that the reversible capacity loss is little, thereby remedied the large problem of irreversible capacity loss, electric conductivity generally can coat to promote by follow-up carbon.
In preparation method of the present invention, the temperature and time of experiment reaction has a great impact composition, structure, size, the pattern tool of product, and the composition of product, structure, size, pattern are pair very large with the lithium cell cathode material performance impact, thereby affect silicon monoxide first charge-discharge efficiency, specific capacity and cycle performance etc.
The present invention compared with prior art has following outstanding advantage and beneficial effect:
(1) preparation technology of the present invention simple, with low cost, be suitable for suitability for industrialized production.
(2) the present invention adopts lithium salts and silicon monoxide to carry out solid phase reaction, and is safe and reliable, and easily large-scale production, and generation can be alleviated the silicates basal body of Volumetric expansion, Effective Raise stable circulation performance; In addition, the present invention adopts raw material to be micron level, easily processing and do not reunite.
(3) chemical property of lithium ion battery negative material of the present invention is excellent, first charge-discharge efficiency is high, specific capacity is high (to be reached more than the 800mAh/g first, present business-like graphite theoretical capacity is 372mAh/g), good cycle, solved successfully that the irreversible capacity loss that silica-base material exists is large when reality prepares the application of lithium ion battery negative, poor electric conductivity and the poor problem of cyclical stability.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of single silica.
Fig. 2 is the XRD collection of illustrative plates of product in embodiment 1 step (2).
Fig. 3 is the XRD collection of illustrative plates of product in comparative example's step (2).
Fig. 4 is the charge-discharge performance figure of simulated battery 1.
Fig. 5 is the charge-discharge performance figure of simulated battery 2.
Fig. 6 is the charge-discharge performance figure of simulated battery 3.
Fig. 7 is the charge-discharge performance figure of simulated battery 4.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) take by weighing respectively the silicon monoxide (200 order) of 5g, the lithium carbonate of 2.1g places the mortar ground and mixed even, obtains mixture.
(2) the mixture 7.1g that step (1) is made is transferred in the corundum crucible, subsequently crucible is put into tube furnace, passes into high pure nitrogen, is warming up to 800 ℃ of heating 12h with 2 ℃/min speed, obtains product.
The product that obtains is carried out the XRD collection of illustrative plates to be detected, testing result as shown in Figure 2, this collection of illustrative plates three strongest ones peak and lithium metasilicate standard card JCPDSno.17-0197 and lithium metasilicate standard card JCPDSno.29-0829 match, and the feature broad peak (the XRD collection of illustrative plates of pure silicon monoxide as shown in Figure 1) that ° has silicon monoxide in 2 θ=10～40 illustrates that silicon monoxide participates in reaction fully.Testing result shows that silicon monoxide and lithium carbonate reaction have generated lithium metasilicate and lithium metasilicate, and concrete reaction equation is as follows:
2SiO+2Li
2CO
3→Li
4SiO
4+Si+2CO
2↑
2SiO+Li
2CO
3→Li
2SiO
3+Si+CO
2↑。
Can be inferred by above-mentioned reaction equation, course of reaction is attended by a small amount of elemental silicon and generates.
(3) product that 5g step (2) is made is mixed and adds in the stainless steel jar mill with 5g graphite 319, the zirconia ball that adds again 150g, ball milling 10h under the 400r/min rotating speed, ball milling namely obtains the silica-based lithium salts composite negative pole material of lithium ion battery after finishing.
(4) the silica-based lithium salts composite negative pole material of lithium ion battery that 1.875g step (3) is made is 0.031g/ml with the binding agent LA132(agglomerant concentration of 8ml), the conductive black of 0.375g evenly mixes, the furnishing slurry, be coated on the Copper Foil, coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 1 through 110 ℃ of dryings of vacuum 8 hours, roll-in (thickness is 80 microns).
Embodiment 2
(1) take by weighing respectively 5g silicon monoxide (200 order), the 3.92g lithium nitrate places the mortar ground and mixed even, obtains mixture.
(2) mixture that 8.92g step (1) is made is transferred in the corundum crucible, subsequently crucible is put into tube furnace, pass into high pure nitrogen, be warming up to 600 ℃ (lithium nitrates 600 ℃ can react) and heat 24h with the speed of 5 ℃/min, obtain product.
(3) product that 5g step (2) is made is mixed and adds in the stainless steel jar mill with the graphite 319 of 5g, add again the 100g zirconia ball, ball milling 20h under the 200r/min rotating speed, ball milling namely obtains the silica-based lithium salts composite negative pole material of lithium ion battery after finishing.
(4) the silica-based lithium salts composite negative pole material of lithium ion battery that 2g step (3) is made is 0.031g/ml with the binding agent LA132(agglomerant concentration of 8ml), the conductive black of 0.25g evenly mixes, the furnishing slurry, be coated on the Copper Foil, coating thickness is 180 microns, and is prepared into anode plate for lithium ionic cell 2 through 50 ℃ of dryings of vacuum 24 hours, roll-in (thickness is 75 microns).
Embodiment 3
(1) take by weighing respectively 5g silicon monoxide (325 order), the 2.72g lithium hydroxide places the mortar ground and mixed even, obtains mixture.
(2) mixture that 7.27g step (1) is made is transferred in the corundum crucible, subsequently crucible is put into tube furnace, passes into high pure nitrogen, is warming up to 500 ℃ of heating 6h with 4 ℃/min speed, obtains product.
(3) product that 5g step (2) is made is mixed and adds in the stainless steel jar mill with 2.5g graphite 319, the zirconia ball that adds again 100g, ball milling 15h under the 400r/min rotating speed, ball milling namely obtains the silica-based lithium salts composite negative pole material of lithium ion battery after finishing.
(4) the silica-based lithium salts composite negative pole material of lithium ion battery that 2.215g step (3) is made is 0.031g/ml with 8ml binding agent LA132(agglomerant concentration), the 0.125g conductive black evenly mixes, the furnishing slurry, be coated on the Copper Foil, coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 3 through 110 ℃ of dryings of vacuum 8 hours, roll-in (thickness is 150 microns).
The comparative example
(1) take by weighing respectively the silicon monoxide (200 order) of 5g, the lithium carbonate of 8.4g places the mortar ground and mixed even, obtains mixture.
(2) the mixture 13.4g that step (1) is made is transferred in the corundum crucible, subsequently crucible is put into tube furnace, passes into high pure nitrogen, is warming up to 800 ℃ of heating 6h with 2 ℃/min speed, obtains product.
The product that obtains is carried out the XRD collection of illustrative plates to be detected, testing result as shown in Figure 3, this collection of illustrative plates three strongest ones peak and lithium metasilicate standard card JCPDSno.17-0197 match, the feature broad peak of silicon monoxide not in 2 θ=10～40 °, testing result shows that silicon monoxide and lithium carbonate react completely and generated lithium metasilicate, and concrete reaction equation is as follows:
2SiO+2Li
2CO
3→Li
4SiO
4+Si+2CO
2↑。
Can be inferred by above-mentioned reaction equation, course of reaction is attended by a small amount of elemental silicon and generates.
(3) product that 5g step (2) is made is mixed and adds in the stainless steel jar mill with the 5g native graphite, the zirconia ball that adds again 150g, ball milling 10h under the 400r/min rotating speed, ball milling namely obtains the silica-based lithium salts composite negative pole material of lithium ion battery after finishing.
(4) the silica-based lithium salts composite negative pole material of lithium ion battery that 2g step (3) is made is 0.031g/ml with the binding agent LA132(agglomerant concentration of 8ml), the conductive agent Super-P of 0.25g evenly mixes, the furnishing slurry, be coated on the Copper Foil, coating thickness is 100 microns, and is prepared into anode plate for lithium ionic cell 4 through 110 ℃ of dryings of vacuum 8 hours, roll-in (thickness is 80 microns).
Effect embodiment
Resulting anode plate for lithium ionic cell 1～4 among embodiment 1～3 and the comparative example is assembled into simulated battery 1～4, and concrete operations and condition are: respectively take microporous polypropylene membrane as barrier film, and 1mol/L LiPF
6Solution be electrolyte, the used organic solvent of electrolyte is to be comprised of the by volume 1:1:1 proportioning mixing of solvent ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), the lithium sheet is to electrode, assembles to obtain in being full of the glove box of argon gas.
Simulated battery is carried out 1～4 carry out performance test, adopt the respectively charging and discharging capacity cycle performance of test simulation battery 1～4 of (Wuhan Jin Nuo Electronics Co., Ltd.) LAND battery test system, wherein, electric current with 0.5mA carries out the experiment of constant current charge-discharge specific capacity loop test, and charging/discharging voltage is limited in 0.001～1.5V.
Test result is as follows:
Simulated battery 1 discharge and recharge data shown in following table one:
30 times of table one simulated battery 1 circulations discharge and recharge data
Simulated battery 2 discharge and recharge data shown in following table two:
30 times of table two simulated battery 2 circulations discharge and recharge data
Simulated battery 3 discharge and recharge data shown in following table three:
30 times of table three simulated battery 3 circulations discharge and recharge data
Simulated battery 4 discharge and recharge data shown in following table four:
30 times of table four simulated battery 4 circulations discharge and recharge data
Table one～four data are drawn, after the corresponding conversion shown in Fig. 4～7, wherein:
Fig. 4 is the charge-discharge performance figure of simulated battery 1, and the lithium ion battery specific capacity of simulated battery 1 is high as seen from the figure, and specific discharge capacity first is 794mAh/g, and the charge ratio capacity is 425mAh/g, and cycle efficieny is 53% first.Through 30 weeks, specific capacity also remains on more than the 406mAh/g, good cycle.
Fig. 5 is the charge-discharge performance figure of simulated battery 2, and the lithium ion battery specific capacity of simulated battery 1 is high as seen from the figure, and specific discharge capacity first is 820mAh/g, and the charge ratio capacity is 453mAh/g, and cycle efficieny is 55% first.Through 30 weeks, specific capacity also remains on more than the 430mAh/g, good cycle.
Fig. 6 is the charge-discharge performance figure of simulated battery 3, and the lithium ion battery specific capacity of simulated battery 3 is high as seen from the figure, and specific discharge capacity first is 834mAh/g, and the charge ratio capacity is 422mAh/g, and cycle efficieny is 50% first.Through 30 weeks, specific capacity also remains on more than the 405mAh/g, good cycle.
Fig. 7 is the charge-discharge performance figure of simulated battery 4, and the lithium ion battery specific capacity of simulated battery 4 is lower as seen from the figure, and specific discharge capacity first is 766mAh/g, and the charge ratio capacity loss is to 244mAh/g, and cycle efficieny only is 31% first.Circulated for 30 weeks, specific capacity only remains on more than the 230mAh/g.
The cycle performance of simulated battery 4 is better, mainly is owing to reacting the lithium metasilicate Stability Analysis of Structures that generates, and has alleviated the Volumetric expansion of active material.But charging and discharging capacity is very low, and this is because in charge and discharge process, the native graphite that adds in a small amount of elemental silicon that active material only generates for reaction and the mechanical milling process.
The charging and discharging capacity of simulated battery 1～3 is higher than simulated battery 4, this mainly is because a small amount of elemental silicon of active material for generating in the silicon monoxide of not participating in reaction fully and the course of reaction in the contained ion cathode material lithium in the anode plate for lithium ionic cell 1～3, and the native graphite of the adding in the mechanical milling process.And contain lithium metasilicate and the lithium metasilicate that effectively to alleviate Volumetric expansion in the negative material, these materials are in the removal lithium embedded process, well alleviated the Volumetric expansion of active material, a good passage is provided for the transportation of lithium ion, so can show excellent chemical property.
Above-described embodiment is the better execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. the preparation method of the silica-based lithium salts composite negative pole material of lithium ion battery is characterized in that comprising following concrete preparation process:
(1) be that the ratio of 1.2～2.4:1 is mixed and ground and evenly obtains mixture in mass ratio with silicon monoxide, lithium salts;
(2) mixture that step (1) is made places reactor, passes into inert gas and is warming up to 500 ℃～800 ℃ afterreaction 6～24h in reactor, obtains product;
(3) product that step (2) is made and graphite-like material with carbon element are 1:(0.5～1 in mass ratio) ratio mix, the gained mixture is mechanical ball milling 8～30h under 200～400rpm/min rotating speed, obtains the silica-based lithium salts composite negative pole material of lithium ion battery.
2. the preparation method of the silica-based lithium salts composite negative pole material of lithium ion battery according to claim 1 is characterized in that:
In the step (1), described lithium salts is 500 ℃～800 ℃ lower decomposable lithium salts; Described silicon monoxide is 200～325 order granular sizes;
In the step (2), described inert gas is 500 ℃～800 ℃ lower inactive gases; Described intensification heats up for the speed with 2～5 ℃/min;
In the step (3), described graphite-like material with carbon element is a kind of in native graphite, electrographite or the modified graphite; The mixture of described product and graphite-like material with carbon element adds zirconia ball before ball milling, wherein, the ratio of grinding media to material of zirconia ball and mixture is 10～15:1 proportioning in mass ratio.
3. the preparation method of the silica-based lithium salts composite negative pole material of lithium ion battery described in according to claim 2 is characterized in that:
In the step (1), described lithium salts is a kind of in lithium hydroxide, lithium carbonate or the lithium nitrate;
In the step (2), described inert gas is a kind of in the nitrogen of purity 99.999% or the argon gas.
4. the silica-based lithium salts composite negative pole material of lithium ion battery is prepared by the preparation method of the silica-based lithium salts composite negative pole material of each described lithium ion battery of claim 1～3.
5. the application of the silica-based lithium salts composite negative pole material of lithium ion battery claimed in claim 4 in the preparation anode plate for lithium ionic cell, it is characterized in that comprising following concrete steps: with the silica-based lithium salts composite negative pole material of described lithium ion battery and binding agent, conductive agent in mass ratio (75～85): (15～5): 10 evenly mix, be coated on the Copper Foil behind the furnishing slurry, and through vacuumize 5～24 hours, roll-in, obtain anode plate for lithium ionic cell.
6. the application of the silica-based lithium salts composite negative pole material of lithium ion battery according to claim 5 in the preparation anode plate for lithium ionic cell is characterized in that: the silica-based lithium salts composite negative pole material of described lithium ion battery and binding agent, conductive agent are by being in mass ratio the 80:10:10 proportioning.
7. the silica-based lithium salts composite negative pole material of lithium ion battery according to claim 5 is characterized in that in the application of preparation in the anode plate for lithium ionic cell: described binding agent is a kind of in binding agent LA132 or the polyvinylidene fluoride.
8. the application of the silica-based lithium salts composite negative pole material of lithium ion battery according to claim 5 in the preparation anode plate for lithium ionic cell is characterized in that:
Described conductive agent is a kind of in conductive black or the nano-sized carbon;
The thickness of described coating is 100～180 microns;
The thickness of described roll-in is 75～150 microns;
Described vacuum drying temperature is 50 ℃～110 ℃.
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| CN108269979A (en) * | 2017-12-28 | 2018-07-10 | 合肥国轩高科动力能源有限公司 | A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof |
| WO2018214050A1 (en) * | 2017-05-24 | 2018-11-29 | Robert Bosch Gmbh | Anode composition and method for prelithiating anode |
| CN109428064A (en) * | 2017-08-28 | 2019-03-05 | 内蒙古欣源石墨烯科技有限公司 | A kind of high performance lithium ionic cell cathode material and preparation method thereof |
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| CN114804116A (en) * | 2021-01-28 | 2022-07-29 | 中国科学院青岛生物能源与过程研究所 | Modified preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN114975901A (en) * | 2021-04-30 | 2022-08-30 | 广汽埃安新能源汽车有限公司 | Negative electrode material and preparation method thereof, lithium ion battery negative electrode, lithium ion battery and preparation method thereof, and lithium ion battery pack |
| CN115706220A (en) * | 2021-08-16 | 2023-02-17 | 北京大学 | Preparation method of novel oxysulfide and application of novel oxysulfide to negative electrode of lithium battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969409A (en) * | 2004-04-15 | 2007-05-23 | Fmc公司 | Composite materials of nano-dispersed silicon and tin and methods of making the same |
| JP2009277485A (en) * | 2008-05-14 | 2009-11-26 | Toyota Motor Corp | METHOD OF MANUFACTURING Si/C COMPLEX TYPE NEGATIVE ELECTRODE ACTIVE MATERIAL |
-
2012
- 2012-10-09 CN CN2012103801591A patent/CN102881870A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969409A (en) * | 2004-04-15 | 2007-05-23 | Fmc公司 | Composite materials of nano-dispersed silicon and tin and methods of making the same |
| JP2009277485A (en) * | 2008-05-14 | 2009-11-26 | Toyota Motor Corp | METHOD OF MANUFACTURING Si/C COMPLEX TYPE NEGATIVE ELECTRODE ACTIVE MATERIAL |
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