CN103996835A - Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material - Google Patents
Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material Download PDFInfo
- Publication number
- CN103996835A CN103996835A CN201410263579.0A CN201410263579A CN103996835A CN 103996835 A CN103996835 A CN 103996835A CN 201410263579 A CN201410263579 A CN 201410263579A CN 103996835 A CN103996835 A CN 103996835A
- Authority
- CN
- China
- Prior art keywords
- silicon
- silane coupler
- based anode
- anode material
- silicon based
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a silicon-base negative material with a silane coupling agent cladding layer structure as well as a preparation method and application of the material. The silicon-base negative material is characterized in that monomer silicon is used as a substrate, and the substrate is coated with a silane coupling agent decorative layer. The preparation method comprises the following steps: ultrasonically blending the silane coupling agent and silicon powder, refluxing the mixture of the silane coupling agent and the silicon powder in a protection atmosphere at a given temperature, and decorating the silicon powder; and washing, suction-filtering and vacuum-drying the mixed solution. When being doped in graphite, the silicon-base negative material with the silane coupling agent cladding layer prepared through the method can be used for preparing a negative material of a lithium ion battery. The silicon powder is modified by utilizing the silane coupling agent, a cladding decorative layer is formed on the surface of the silicon substrate, and due to the bridging effect of the silane coupling agent, the silicon substrate is tightly combined with a conductive polymer on the outermost layer, so that the expansion pulverization effect of the silicon material can be effectively prevented, and the silicon-base negative material is high in primary coulombic efficiency, good in cycling stability and capable of meeting the requirements of a power battery.
Description
Technical field
The invention belongs to lithium ion battery negative material and technical field of electrochemistry, relate to a kind of silicon based anode material with silane coupler coating layer structure and preparation method thereof and application.
Background technology
In the last few years, lithium ion battery with respect to the secondary cells such as traditional lead-acid battery, iron cell, Ni-MH battery have high-energy-density, high output voltage, low self-discharge, memory effect is little and advantages of environment protection, and be widely used and study.The performance of lithium ion battery critical material is the important deciding factor of battery performance, and it is global scientific research focus that the exploitation of negative material improves.The negative materials such as silicon materials, material with carbon element, tin material, lithium titanate, metal oxide are studied widely.But there is the defects such as cycle performance is poor, specific energy density is low, cost is high, poor stability, consistency problem in the lithium-ion battery system of these negative material assemblings, is difficult to meet the requirement of power energy-storage battery.
Silicon based anode material is because its theoretical specific capacity surpasses 4200 mAh/g, embedding lithium current potential is low, actual specific capacity is greater than 3000 mAh/g, at natural rich content, the advantages such as cost of material is relatively cheap are the study hotspots of lithium ion battery negative material always.The shortcoming severe inhibition such as but coulomb efficiency first of silicon materials is low, high rate performance is poor, cycle performance is poor the large-scale application of silicon based anode material in lithium ion battery.
For the silicon based anode material of development cycle excellent performance, researcher has developed multiple technologies means silicon materials has been carried out to modification raising.Graphite, hard carbon, pitch, carbon nano-tube, carbon nano-fiber, metal nano-tube etc. have been used to coated silicon based anode material.As N. Kurita etc. makes the Si with regular texture
2c
52h
18, this material is with respect to C
54h
18can embed in a large number lithium ion, and its structure also can reduce the irreversible reaction that lithium ion is deviate from, there is good cycle performance.N. the employing hot gas sedimentation such as Dimov has been coated one deck material with carbon element on elementary silicon surface, obtain the particle that average-size is 18 μ m, specific capacity is more than 600mAh/g, than the theoretical specific capacity of material with carbon element (372 mAh/g) height, cycle performance and material with carbon element are suitable, with elemental silicon, compare and improve a lot.Z. S. Wen etc., by carrying out pyrolysis to inserting the resin of graphite and elemental silicon, obtains silicon-carbon compound, and its specific capacity reaches 800～900 mAh/g, circulates after 20 times, and its specific capacity is stabilized in 600 mAh/g.B.J. Neudecker etc. makes SiSn
0.87o
1.20n
1.72, specific capacity approaches 800 mAh/g, after discharging and recharging for 10000 times, still can remain on 600 mAh/g, and discharge voltage 4.1～2.7V circulates irreversible capacity loss in 0.002% at every turn, but too high cost has hindered its business-like process.
Silane coupler is that people study the earliest, apply coupling agent the earliest, has advantages of that consumption is few, cost is low.Owing to having X and R two class chemical groups in silane coupled agent molecule simultaneously, wherein R is the organo-functional group that can be combined with high molecular polymer; X be can with silicon surface oxidation layer in the hydrolyzable groups of hydroxyl reaction.Therefore the effect of coupling is played in the interaction of silane coupler between high molecular polymer and inorganic system.
Therefore, need at present the modification method and the preparation method that find a kind of simple silicon based anode material badly, make silicon based anode material have both higher coulomb efficiency first and good cyclical stability simultaneously, thereby can meet the requirement of electrokinetic cell.
Summary of the invention
The object of the present invention is to provide a kind of silicon based anode material with silane coupler coating layer structure and preparation method thereof and application, use silane coupler to modify silica flour, silane coupler can improve silicon-based anode in charge and discharge cycles expansion atomizing, the method is simple, low cost of manufacture, favorable reproducibility, is convenient to large-scale industrial production.
The object of the invention is to be achieved through the following technical solutions:
A silicon based anode material with silane coupler coating layer structure, take elemental silicon as substrate, in substrate, is coated with silane coupler decorative layer.
An above-mentioned preparation method with the silicon based anode material of silane coupler coating layer structure, its step is as follows:
(1) silane coupler and silica flour are carried out to ultrasonic blend in ethanol-water system, in protective atmosphere, under uniform temperature, reflux, silica flour is modified; Wherein: the preparation method of silica flour is a kind of of vapor phase method, sol-gel processing, the precipitation method, microemulsion method, ball-milling method; The particle size interval scope of silica flour is between 20 to 8000 nm; Silane coupler is a kind of of γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, dimethyldimethoxysil,ne, methyl tributanoximo silane, isocyanic acid propyl-triethoxysilicane; The addition of silane coupler is the 0.01-10% of silica flour mass fraction; Reflux temperature is 40-120 ℃, and return time is 5-10 h;
(2), by described mixed solution washing, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler coating layer structure; Wherein: vacuumize temperature is 45-55 ℃, the vacuumize time is 10-12 h.
The silicon based anode material with silane coupler coating layer structure prepared by said method is entrained in the negative material that can be used for preparing lithium ion battery in graphite, and the silicon based anode material wherein with silane coupler coating layer structure accounts for 1 ~ 98% of content of graphite.
The silane coupler modified silica flour of the present invention, on silicon base surface, form coating decoration layer, function served as bridge due to silane coupler, silicon base and outermost conducting polymer are in conjunction with tight, the expansion efflorescence effect that can effectively stop silicon materials, make silicon based anode material there is higher coulomb efficiency first and good cyclical stability, to meet the requirement of electrokinetic cell.
Advantage of the present invention is as follows:
(1) with silane coupler, modify elemental silicon to form coating layer, improved coulomb efficiency and the cyclical stability first of silicon based anode material, can meet the requirement of electrokinetic cell.
(2) this modified technique is applicable to all silicon based anode materials, simple, low cost of manufacture, and favorable reproducibility, is convenient to large-scale industrial production.
(3) silicon-based anode of the present invention is for the silicon-based anode of prior art, there is higher specific capacity, particularly the cycle performance of existing silicium cathode has been carried out improving significantly, after being entrained in graphite, the performance of graphite cathode material has been had significantly and promoted.
(4) the prepared silicon based anode material of the present invention has infrared spectrum as shown in Figure 5, and its characteristic peak is 2972cm
-1, 2926cm
-1and 1735cm
-1.
Accompanying drawing explanation
Fig. 1 is the reaction principle figure of silane coupler and elemental silicon substrate;
Fig. 2 is the infrared spectrum with the silicon based anode material of silane coupler coating layer;
Fig. 3 is the SEM figure of silane coupler modified front silicon based anode material;
Fig. 4 is the SEM figure of the silicon based anode material (embodiment 1) of silane coupler coating layer structure;
Fig. 5 is the silicon based anode material cycle performance curve of silane coupler coating layer structure.
Embodiment
Below by embodiment and comparative example, further illustrate the present invention, these embodiment, just for the present invention is described, the invention is not restricted to following examples.Every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1:
1,0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, for 200mL/min, temperature, be the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification.
Fig. 1 has explained the reaction principle of silane coupler and elemental silicon substrate, after silane coupler hydrolysis, sloughs a hydrone, will between silicon atom, be joined to one another, and forms network structure.
Fig. 2 is the infrared spectrum with the silicon based anode material of silane coupler coating layer.In silane coupler γ-(methacryloxypropyl) propyl trimethoxy silicane molecule, containing alkoxyl, contain carbon carbon unsaturated double-bond simultaneously.As can be seen from Figure 2, material modified at 2972 and 2926 cm after the modification of γ-(methacryloxypropyl) propyl trimethoxy silicane
-1there is absworption peak in place, this absworption peak correspondence the stretching vibration of c h bond.
In comparative example, the comparatively serious (see figure 3) of silica flour reunion, and the spheroid (see figure 4) that the silicon based anode material with silane coupler coating layer of preparation is particle integrity, reunion situation has obtained alleviation, and granular size is about 20-8000 nm.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, initial charge capacity 2839 mAh/g of material, first charge-discharge efficiency is 72%, after 200 circulations, charging capacity is 1801.84mAh/g, Capacitance reserve, in 1800 mAh/g left and right, has excellent performance.
embodiment 2:
1,0.25g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, for 200mL/min, temperature, be that reflux under 60 ℃, magnetic agitation condition 10 h, temperature are vacuumize 12h at 55 ℃; finally obtain the silicon based anode material of γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane surface modification.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, initial charge capacity 2687 mAh/g of material, first charge-discharge efficiency is 71.8%, after 200 circulations, charging capacity is 1898.95 mAh/g, Capacitance reserve, in 1900 mAh/g left and right, has excellent performance.
embodiment 3:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, be that 200 mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, initial charge capacity 2695.17 mAh/g of material, first charge-discharge efficiency is 72.7%, after 200 circulations, charging capacity is 1941.59mAh/g, Capacitance reserve, in 1940 mAh/g left and right, has excellent performance.
embodiment 4:
1,0.5g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, for 200mL/min, temperature, be that reflux under 60 ℃, magnetic agitation condition 10 h, temperature are vacuumize 12h at 55 ℃; finally obtain the silicon based anode material of γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane surface modification.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, initial charge capacity 2417.28 mAh/g of material, first charge-discharge efficiency is 72.1%, after 200 circulations, charging capacity is 1718.21 mAh/g, Capacitance reserve, in 1700 mAh/g left and right, has excellent performance.
embodiment 5:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, be that 200 mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, after mass fraction ratio with 20% joins in graphite, this composite material has good cycle performance, initial charge capacity 836.64 mAh/g of material, first charge-discharge efficiency is 85.7%, after 200 circulations, charging capacity is 764.19mAh/g, and Capacitance reserve, in 760 mAh/g left and right, has excellent performance.
embodiment 6:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 5g silica flour ultrasonic mixing 0.5h;
2, by the material mixing in step 1, in shielding gas flow speed, be that 200 mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification.
3, after the silicon based anode material of the γ making in step 2-(methacryloxypropyl) propyl trimethoxy silicane surface modification is mixed with graphite with 50% additional proportion, can be used as a kind of Novel cathode material for lithium ion battery, replace traditional lithium ion battery negative material.
Silicon based anode material cycle performance curve from Fig. 5 silane coupler coating layer structure, after mass fraction ratio with 50% joins in graphite, this composite material has good cycle performance, initial charge capacity 1533.59 mAh/g of material, first charge-discharge efficiency is 79.32%, after 200 circulations, charging capacity is 1411.02 mAh/g, and Capacitance reserve, in 1411.02 mAh/g left and right, has excellent performance.
Comparative example: undressed elemental silicon.
The test case contrast of each embodiment and comparative example is as shown in table 1.
Table 1
Claims (9)
1. a silicon based anode material with silane coupler coating layer structure, is characterized in that described silicon based anode material take elemental silicon as substrate, in substrate, is coated with silane coupler decorative layer.
2. a preparation method with the silicon based anode material of silane coupler coating layer structure claimed in claim 1, is characterized in that described method step is as follows:
(1) silane coupler and silica flour are carried out to ultrasonic blend, in protective atmosphere, at 40-120 ℃ of temperature, reflux, silica flour is modified; Wherein: the addition of silane coupler is the 0.01-10% of silica flour mass fraction;
(2), by described mixed solution washing, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler coating layer structure.
3. the preparation method with the silicon based anode material of silane coupler coating layer structure according to claim 2, the preparation method who it is characterized in that described silica flour is a kind of of vapor phase method, sol-gel processing, the precipitation method, microemulsion method, ball-milling method.
4. according to the preparation method of the silicon based anode material with silane coupler coating layer structure described in claim 2 or 3, it is characterized in that the particle size interval scope of described silica flour is between 20 to 8000 nm.
5. the preparation method with the silicon based anode material of silane coupler coating layer structure according to claim 2, it is characterized in that described silane coupler is a kind of of γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, dimethyldimethoxysil,ne, methyl tributanoximo silane, isocyanic acid propyl-triethoxysilicane.
6. the preparation method with the silicon based anode material of silane coupler coating layer structure according to claim 2, is characterized in that described return time is 5-10 h.
7. the preparation method with the silicon based anode material of silane coupler coating layer structure according to claim 2, is characterized in that described vacuumize temperature is 45-55 ℃, and the vacuumize time is 10-12 h.
8. the silicon based anode material with silane coupler coating layer structure claimed in claim 1 is entrained in graphite the application as lithium ion battery negative material.
9. the silicon based anode material with silane coupler coating layer structure according to claim 8 is entrained in graphite as the application of lithium ion battery negative material, it is characterized in that described silicon based anode material accounts for 1 ~ 98% of content of graphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410263579.0A CN103996835A (en) | 2014-06-14 | 2014-06-14 | Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410263579.0A CN103996835A (en) | 2014-06-14 | 2014-06-14 | Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103996835A true CN103996835A (en) | 2014-08-20 |
Family
ID=51310920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410263579.0A Pending CN103996835A (en) | 2014-06-14 | 2014-06-14 | Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103996835A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN104852050A (en) * | 2015-06-03 | 2015-08-19 | 哈尔滨工业大学 | Silane compound modified SiO anode material as well as preparation method and application thereof |
| CN105514382A (en) * | 2015-12-29 | 2016-04-20 | 哈尔滨工业大学 | Preparing method and application of silicon-based negative electrode material with SiO2 coating layer |
| CN106876689A (en) * | 2017-03-24 | 2017-06-20 | 中航锂电（洛阳）有限公司 | A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery |
| CN107403910A (en) * | 2016-05-20 | 2017-11-28 | 通用汽车环球科技运作有限责任公司 | For forming the polymerization technique of polymer ultra-thin conforma coating on electrode material |
| CN108028376A (en) * | 2015-09-24 | 2018-05-11 | 松下知识产权经营株式会社 | Anode for nonaqueous electrolyte secondary battery active material and anode |
| CN108155370A (en) * | 2016-12-02 | 2018-06-12 | 罗伯特·博世有限公司 | There are the anode active material particles of SEI layers of synthesis by the polymerization of main chain method is grafted to |
| CN110120506A (en) * | 2019-05-08 | 2019-08-13 | 福州大学 | A kind of preparation method of graphite silicon nanocomposite |
| CN110581271A (en) * | 2019-10-15 | 2019-12-17 | 浙江锂宸新材料科技有限公司 | Modified silicon negative electrode material for lithium ion battery and preparation method and application thereof |
| CN110890538A (en) * | 2019-11-14 | 2020-03-17 | 浙江锂宸新材料科技有限公司 | Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material |
| CN112290004A (en) * | 2020-11-06 | 2021-01-29 | 江苏厚生新能源科技有限公司 | Expansion-resistant composite silicon, expansion-resistant composite silicon intermediate, preparation method and lithium battery |
| CN112349888A (en) * | 2019-08-07 | 2021-02-09 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112778754A (en) * | 2021-01-28 | 2021-05-11 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| WO2021189407A1 (en) * | 2020-03-27 | 2021-09-30 | 宁德新能源科技有限公司 | Negative electrode active material, and electrochemical device and electronic device using same |
| CN114024023A (en) * | 2021-10-21 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | All-solid-state lithium metal battery with high-strength and high-conductivity negative electrode coupling interface |
| EP4047684A4 (en) * | 2019-10-18 | 2024-01-03 | Murata Manufacturing Co | Negative electrode active material, negative electrode, and secondary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505187A (en) * | 2002-11-26 | 2004-06-16 | 信越化学工业株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, making method, and lithium ion secondary battery |
| JP2011011928A (en) * | 2009-06-30 | 2011-01-20 | Nissan Motor Co Ltd | Surface-modified silicon particle |
| CN102687314A (en) * | 2009-12-24 | 2012-09-19 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary cell |
| CN103441247A (en) * | 2013-08-15 | 2013-12-11 | 广州市香港科大***研究院 | High-performance silicon/graphene oxide negative electrode material based on chemical bond and preparation method thereof |
-
2014
- 2014-06-14 CN CN201410263579.0A patent/CN103996835A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505187A (en) * | 2002-11-26 | 2004-06-16 | 信越化学工业株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, making method, and lithium ion secondary battery |
| JP2011011928A (en) * | 2009-06-30 | 2011-01-20 | Nissan Motor Co Ltd | Surface-modified silicon particle |
| CN102687314A (en) * | 2009-12-24 | 2012-09-19 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary cell |
| CN103441247A (en) * | 2013-08-15 | 2013-12-11 | 广州市香港科大***研究院 | High-performance silicon/graphene oxide negative electrode material based on chemical bond and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 任丽 等: "APS对PPy/SiO2纳米到带你复合材料的界面改性研究", 《功能材料》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN104852050A (en) * | 2015-06-03 | 2015-08-19 | 哈尔滨工业大学 | Silane compound modified SiO anode material as well as preparation method and application thereof |
| CN104852050B (en) * | 2015-06-03 | 2017-09-01 | 哈尔滨工业大学 | A kind of silane compound modification SiO negative materials and preparation method and application |
| CN108028376A (en) * | 2015-09-24 | 2018-05-11 | 松下知识产权经营株式会社 | Anode for nonaqueous electrolyte secondary battery active material and anode |
| CN108028376B (en) * | 2015-09-24 | 2021-08-27 | 松下知识产权经营株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery and negative electrode |
| CN105514382A (en) * | 2015-12-29 | 2016-04-20 | 哈尔滨工业大学 | Preparing method and application of silicon-based negative electrode material with SiO2 coating layer |
| CN107403910B (en) * | 2016-05-20 | 2020-11-10 | 通用汽车环球科技运作有限责任公司 | Polymerization process for forming polymer ultra-thin conformal coatings on electrode materials |
| CN107403910A (en) * | 2016-05-20 | 2017-11-28 | 通用汽车环球科技运作有限责任公司 | For forming the polymerization technique of polymer ultra-thin conforma coating on electrode material |
| US10991946B2 (en) | 2016-05-20 | 2021-04-27 | GM Global Technology Operations LLC | Polymerization process for forming polymeric ultrathin conformal coatings on electrode materials |
| CN108155370A (en) * | 2016-12-02 | 2018-06-12 | 罗伯特·博世有限公司 | There are the anode active material particles of SEI layers of synthesis by the polymerization of main chain method is grafted to |
| CN108155370B (en) * | 2016-12-02 | 2024-04-09 | 罗伯特·博世有限公司 | Polymerization of anode active material particles having synthetic SEI layer by grafting to backbone method |
| CN106876689B (en) * | 2017-03-24 | 2020-02-21 | 中航锂电（洛阳）有限公司 | Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and lithium ion battery |
| CN106876689A (en) * | 2017-03-24 | 2017-06-20 | 中航锂电（洛阳）有限公司 | A kind of nitrogen-doped graphene silicon composite cathode material and preparation method thereof, lithium ion battery |
| CN110120506A (en) * | 2019-05-08 | 2019-08-13 | 福州大学 | A kind of preparation method of graphite silicon nanocomposite |
| CN110120506B (en) * | 2019-05-08 | 2020-12-04 | 福州大学 | Preparation method of graphite silicon nano composite material |
| CN112349888A (en) * | 2019-08-07 | 2021-02-09 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112349888B (en) * | 2019-08-07 | 2022-03-01 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN110581271A (en) * | 2019-10-15 | 2019-12-17 | 浙江锂宸新材料科技有限公司 | Modified silicon negative electrode material for lithium ion battery and preparation method and application thereof |
| EP4047684A4 (en) * | 2019-10-18 | 2024-01-03 | Murata Manufacturing Co | Negative electrode active material, negative electrode, and secondary battery |
| CN110890538B (en) * | 2019-11-14 | 2021-05-25 | 浙江锂宸新材料科技有限公司 | Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material |
| CN110890538A (en) * | 2019-11-14 | 2020-03-17 | 浙江锂宸新材料科技有限公司 | Method for improving initial coulombic efficiency of silicon-based lithium ion battery negative electrode material |
| WO2021189407A1 (en) * | 2020-03-27 | 2021-09-30 | 宁德新能源科技有限公司 | Negative electrode active material, and electrochemical device and electronic device using same |
| CN112290004A (en) * | 2020-11-06 | 2021-01-29 | 江苏厚生新能源科技有限公司 | Expansion-resistant composite silicon, expansion-resistant composite silicon intermediate, preparation method and lithium battery |
| CN112290004B (en) * | 2020-11-06 | 2021-09-07 | 江苏厚生新能源科技有限公司 | Expansion-resistant composite silicon, expansion-resistant composite silicon intermediate, preparation method and lithium battery |
| CN112778754A (en) * | 2021-01-28 | 2021-05-11 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| CN114024023A (en) * | 2021-10-21 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | All-solid-state lithium metal battery with high-strength and high-conductivity negative electrode coupling interface |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103996835A (en) | Silicon-base negative material with silane coupling agent cladding layer structure as well as preparation method and application of material | |
| CN103996834B (en) | A kind of silicon based anode material with silane coupler and conducting polymer double-coating structure and preparation method and application | |
| CN110444750B (en) | Negative electrode material, and electrochemical device and electronic device comprising same | |
| CN103311514B (en) | A kind of preparation method of modification lithium-ion battery graphite cathode material | |
| CN104241621B (en) | The silica-based composite negative pole material of a kind of lithium ion battery | |
| CN110518226B (en) | Silicon-carbon composite negative electrode material and preparation method thereof | |
| CN107275671A (en) | A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite | |
| CN107611406A (en) | A kind of preparation method of silicon/graphene/carbon composite negative pole material | |
| CN103296257B (en) | Preparation method of modified lithium titanate negative material of lithium-ion battery | |
| CN104659366A (en) | Preparation method of anode material for power lithium ion battery | |
| CN103633295A (en) | Silicon-carbon composite material, lithium ion battery, and preparation method and application of silicon-carbon composite material | |
| CN107302082A (en) | Silicium cathode material and preparation method thereof, cathode pole piece and lithium ion battery | |
| CN104779372A (en) | Cyclic utilization method for using graphite fine powder as negative pole material of lithium-ion batteries | |
| CN103311522A (en) | Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same | |
| CN103259005B (en) | A kind of preparation method of high power capacity high rate lithium ionic cell cathode material | |
| CN104538635A (en) | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof | |
| CN105514382A (en) | Preparing method and application of silicon-based negative electrode material with SiO2 coating layer | |
| CN107464926B (en) | Core-shell structure of nano silicon energy storage material and lithium ion battery comprising core-shell structure | |
| CN113066954B (en) | Negative plate and application thereof | |
| CN109309199B (en) | Preparation method of lithium ion battery cathode red phosphorus/carbon nanotube composite material | |
| CN105140483A (en) | Preparation method of modified lithium battery anode material | |
| CN103996836B (en) | A kind of preparation method of alloying silicon based anode material and application | |
| CN104752691B (en) | A kind of Si/C Composite Negative Electrode Material for Lithium Ion Batteries and preparation method thereof | |
| CN104009213B (en) | A kind of preparation method of functional amido silicon based anode material and application | |
| CN115188949B (en) | Preparation method of mesocarbon microbead-silicon carbon composite negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140820 |