CN101740766A - Cathode active material, preparation method thereof and lithium battery using same - Google Patents
Cathode active material, preparation method thereof and lithium battery using same Download PDFInfo
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- CN101740766A CN101740766A CN200810217840A CN200810217840A CN101740766A CN 101740766 A CN101740766 A CN 101740766A CN 200810217840 A CN200810217840 A CN 200810217840A CN 200810217840 A CN200810217840 A CN 200810217840A CN 101740766 A CN101740766 A CN 101740766A
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- 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 provides a cathode active material used for a lithium ion battery, which comprises a dispersion carrier and a composite material dispersing in the dispersion carrier. The dispersion carrier comprises silicon fibers and carbon fibers; and the composite material is a silicon/metal alloy. The conventional silica-based material has the problems of serious volume effect, pulverization and shedding during electrochemical lithium extraction, which causes poor cycle performance of the battery. The cathode active material can effectively solve the problems of the volume effect, the pulverization and the shedding so as to improve the cycle performance of the battery. The invention also provides a method for preparing the cathode active material, which comprises the following steps of: ball-milling and mixing the silicon fibers and the carbon fibers, and sintering the mixture at high temperature to prepare silicon-carbon fibers; ball-milling and mixing silicon and a metal, and sintering the mixture at the high temperature to prepare the silicon/metal alloy; mixing the silicon-carbon fibers and the silicon/metal alloy, adding the mixture into a dispersing agent, and dispersing the mixture with ultrasonic waves to obtain slurry; and volatilizing the dispersing agent in the slurry, and processing the slurry under a shielding gas at low temperature.
Description
Technical field
The lithium battery that the present invention relates to a kind of negative material and preparation method thereof and use this material, the lithium battery that is specifically related to a kind of silicon-based anode active material and preparation method thereof and uses this material.
Background technology
Lithium ion battery becomes the desirable supporting power supply of multiple portable electronic, mobile product owing to have high voltage, high-energy-density, long circulation life and characteristics such as environmentally friendly.
At present, in lithium ion battery, negative maximum adopts carbon-based material more, for example MCMB, graphite, organic RESEARCH OF PYROCARBON etc.Carbon-based material has good reversible removal lithium embedded performance, but its reversible capacity low (＜372mAh/g), and embedding lithium current potential lower (0.25-0.05Vvs.Li+/Li) is near the lithium metal current potential, and the lithium ion diffusion velocity is low, may cause when high power charging-discharging battery security poor.In order to address the above problem, silica-base material occurred, but existing silica-base material to exist the serious bulk effect and the problem of powder of detached when electrochemical lithium takes off embedding, thereby cause the efficient of battery and cycle performance to reduce.
Summary of the invention
Technical problem to be solved by this invention is: serious bulk effect and powder of detached problem when the existing silica-base material of improvement charges and discharge, the cycle performance of raising battery.The invention provides the good negative active core-shell material of a kind of cycle performance of battery.
A kind of negative active core-shell material that is used for lithium ion battery, it comprises dispersible carrier and is scattered in composite material in the dispersible carrier, and described dispersible carrier comprises silica fibre and carbon fiber, and described composite material is silicon/metal alloy.
The invention also discloses a kind of preparation method of negative active core-shell material.
A kind of preparation method of above-mentioned negative active core-shell material, it may further comprise the steps:
(1) silica fibre, mixed being incorporated in of carbon fiber ball milling are protected high temperature sintering under the gas, obtain the silicon-carbon fiber; Silicon, metal ball milling mixed and under protection gas high temperature sintering, obtain silicon/metal alloy;
(2) silicon-carbon fiber and silicon/metal alloy are mixed, add in the dispersant, ultrasonic wave disperses to obtain slurry;
(3) with the volatilization of the dispersant in the slurry, K cryogenic treatment under protection gas.
The invention also discloses a kind of lithium rechargeable battery that adopts above-mentioned negative active core-shell material, it comprises: battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises collector and the positive electrode active materials that loads on the collector, and described negative pole comprises collector and the above-mentioned negative active core-shell material that loads on the collector.
The present inventor is surprised to find that: with silica fibre and the synthetic dispersible carrier of carbon fiber, because the silicon-carbon fiber has its unique space structure, make the stress that produces when lithium ion takes off embedding in charge and discharge process unfold to horizontal and vertical, thereby relaxed gathering of internal stress, can effectively avoid the powder of detached phenomenon.With silicon/metal alloy is the activated centre, and alloy material also can the absorption portion volumetric expansion, and alloy material obviously improved since the characteristic of semiconductor of silicon bring electrically contact problem; This negative active core-shell material is because its unique filled type space structure even because lithium ion embeds in the silicon in a large number, produce 300% volumetric expansion, still can keep excellent electric contact.
Negative active core-shell material provided by the present invention has kept the high capacity characteristics of silicon, has improved the energy density of lithium ion battery negative active material, the change in volume of overall electrode is effectively weakened, and increased its cyclical stability.
Embodiment
A kind of negative active core-shell material that is used for lithium ion battery, it comprises dispersible carrier and is scattered in composite material in the dispersible carrier, and described dispersible carrier comprises silica fibre and carbon fiber, and described composite material is silicon/metal alloy.
It is 100nm that silica fibre of the present invention is preferably its diameter, and average length is 10 μ m.
Described carbon fiber is a conductive carbon fibre, and it is 100nm that the present invention is preferably its diameter, and average length is 10 μ m.
The mass ratio of carbon fiber and silica fibre is preferably 1 in the described dispersible carrier: 1-1: 5.
Silica fibre has higher embedding lithium capacity, but the electric conductivity of silica fibre is not fine; Carbon fiber has good electrical conductivity, but its embedding lithium capacity is low; The mass ratio of carbon fiber and silica fibre is preferably 1: 1-1: 5, and make negative active core-shell material like this and both can keep higher capacity, also have good electrical contact simultaneously.
Described dispersible carrier has spatial skeleton, is the space network structure that silica fibre and carbon fiber high-temperature cross-linking form, and forms the carborundum of part.
Described silicon/metal alloy, the preferred transition metal of metal wherein, more preferably one or more among Fe, Co, Ni, the Cu.
The mol ratio of element silicon and metallic element is 1 in described silicon/metal alloy: 1-1: 5, be preferably mol ratio 1: 2-1: 3.
Described silicon/metal alloy also can be alloy part, and described alloy part is meant and had wherein both contained silicon/metal alloy phase, also contains the metal phase.Alloy phase has wherein had certain specific capacity, can keep higher Capacity Ratio, and metal can strengthen the electrochemistry contact mutually.
The granular size of silicon/metal alloy is 0.1 μ m-100 μ m.
Described silicon/metal alloy particle is embedded between the cancellated space, space of described dispersible carrier.
The mass ratio of described dispersible carrier and described composite material is 1: 1-1: 10, be preferably 1: 3-1: 5.
A kind of preparation method of above-mentioned negative active core-shell material, it comprises:
(1) silica fibre, mixed being incorporated in of carbon fiber ball milling are protected high temperature sintering under the gas, obtain the silicon-carbon fiber; Silicon, metal ball milling mixed and under protection gas high temperature sintering, obtain silicon/metal alloy;
(2) silicon-carbon fiber and silicon/metal alloy are mixed, add in the dispersant, ultrasonic wave disperses to obtain slurry;
(3) with the volatilization of the dispersant in the slurry, K cryogenic treatment under protection gas.
Described ball milling is mixed into known in those skilled in the art, and the present invention preferably adopts planetary ball mill to carry out ball milling under inert gas such as argon shield.
Silicon, metal ball milling mix the back particle grain size and are controlled between the 0.01-100 μ m.
Described high temperature sintering also is known in those skilled in the art.For example the high temperature sintering of silica fibre, carbon fiber is to react 30-120min down at 600-1000 ℃.The high temperature sintering of silicon, metal is to react 60-240min down at 800-1400 ℃.
Described silicon and metal are Powdered, mainly are meant silica flour, metal powder with electro-chemical activity, and the particle diameter of its powder is preferably micron order, submicron order or nanoscale.
Described silicon-carbon fiber and silicon/metal alloy are mixed into mechanical mixture, and the mixing of silicon-carbon fiber and silicon/metal alloy is preferably according to 1: 1-1: 10 mixed.Silicon/the metal alloy that obtains like this is well-dispersed among the silicon-carbon fiber reinforcement.In charge and discharge process, the volumetric expansion that silicon causes, a part is slowed down by the extension of silicon-carbon fiber, is more absorbed by transition metal.Add that conductive carbon fibre forms the spatial network of silicon-carbon fiber, after expanding, still keep good electrochemistry contact, thereby significantly must improve cycle performance.
Described ultrasonic wave is separated into known in those skilled in the art, and the ultrasonic wave jitter time is 100-300min.
Described volatilization is known in those skilled in the art.For example can be that normal temperature volatilization also can be to volatilize in being lower than 50 ℃ environment.
Described dispersant is meant the effectively organic solvent of dispersion solid particle, and at room temperature has certain volatile organic solvent, for example acetone, oxolane, oxirane etc.The preferred N-methyl pyrrolidone of dispersant of the present invention NMP.
Described K cryogenic treatment is meant that the mixture that will obtain moves in the sealed reaction system, adopts under the inert atmosphere protection, at 100-500 ℃ of insulation 60-180min; Insulation under protective atmosphere, naturally cools to room temperature after finishing.
A kind of lithium rechargeable battery that adopts above-mentioned negative active core-shell material, it comprises: battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises collector and the positive electrode active materials that loads on the collector, and described negative pole comprises collector and the above-mentioned negative active core-shell material that loads on the collector.
In lithium rechargeable battery of the present invention, electrolyte can be nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
In lithium rechargeable battery of the present invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.Described barrier film also can be a polyimide film.Described polyimide film can be polyimide film known in those skilled in the art, and preferably its porosity is 20%-55%, and average pore diameter is the 30-120 nanometer.
In lithium rechargeable battery of the present invention, positive electrode active materials can adopt the positive electrode active materials of various routines, as LiFePO4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F and LiFeO
2In one or more.In order significantly to improve described positive electrode active materials performance, described positive electrode active materials is preferably LiFePO4, LiCoO
2, LiVPO
4Among the F one or more.
The preparation method of lithium rechargeable battery provided by the invention carries out according to method as well known to those skilled in the art, in general, this method comprises anodal, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively, pole piece is inserted in the battery case, add electrolyte, then sealing, wherein, described negative pole comprises collector and the negative active core-shell material that loads on the collector, and wherein, described negative active core-shell material is a negative active core-shell material provided by the invention.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
The present invention is further elaborated below in conjunction with specific embodiment.
Embodiment 1
Take by weighing silica fibre 100g and carbon fiber 200g, send into planetary ball mill, it is 600 commentaries on classics/min that rotating speed is set, the powder that obtains mixing behind the ball milling 120min.With the powder 800 ℃ of high-temperature process 60min under the Ar atmosphere protection that obtain, form the silicon-carbon fiber.
Take by weighing silica flour (particle diameter 5 μ m) 200g and iron powder 600g, send into planetary ball mill, it is 600 commentaries on classics/min that rotating speed is set, the powder that obtains mixing behind the ball milling 120min.With the powder 1000 ℃ of high-temperature process 180min under the Ar atmosphere protection that obtain, form silicon/metal alloy.
Take by weighing above-mentioned synthetic silicon-carbon fiber 200g and silicon/metal alloy 800g, add among the organic solvent NMP, ultrasonic wave disperses 200min, forms slurry.Slurry is volatilized behind the organic solvent, and the mixture that obtains moves in the sealed reaction system, adopts under the Ar atmosphere protection, handles 100min for 300 ℃.Obtain negative active core-shell material, the product note is made G1.
Embodiment 2
Different is to replace iron powder with copper powder with embodiment 1, obtains negative active core-shell material, and the product note is made G2.
Embodiment 3
Different is to take by weighing carbon fiber 50g and silica fibre 250g with embodiment 1, obtains negative active core-shell material, and the product note is made G3.
Embodiment 4
Different is to take by weighing silica flour (5 μ m) 100g and iron powder 500g with embodiment 1, obtains negative active core-shell material, and the product note is made G4.
Embodiment 5
Different is to take by weighing above-mentioned synthetic silicon-carbon fiber 30g and silicon/metal alloy 300g with embodiment 1, obtains negative active core-shell material, and the product note is made G5.
Embodiment 6
(1) Zheng Ji preparation
With 8.8KgN-methyl pyrrolidone (NMP), 1Kg acetylene black and 0.2Kg polyvinylidene fluoride (PVDF) powder, stir and be mixed with the acetylene black wash in 5 minutes.
Get the above-mentioned acetylene black slurry for preparing of 2Kg, add 3KgN-methyl pyrrolidone (NMP), 10Kg cobalt acid lithium (the auspicious auspicious company in Hunan product, particle diameter 8 μ m), 0.3Kg polyvinylidene fluoride (PVDF), stir and promptly get battery anode active material after 20 minutes.
Above-mentioned anode active material of lithium ion battery is coated on the aluminum foil current collector that thickness is 20 μ m, and after drying, roll-in and the cut-parts, making length is that 400mm, width are that 44mm, thickness are the positive plate of 0.15mm.
(2) preparation of negative pole
100Kg negative active core-shell material G1,3Kg adhesive butadiene-styrene latex (SBR), 3Kg carboxymethyl cellulose (CMC) are joined in the 50Kg water, in mixer, stir then and form cathode size stable, homogeneous.This slurry is coated on the Copper Foil that thickness is 20 μ m equably, through 120 ℃ of oven dry, roll-in and cut-parts, is that 410mm, width are that 45mm, thickness are the negative plate of 0.18mm thereby make length.
(3) assembling of battery
The positive plate that (1) is obtained, negative plate and the PP/PE/PP barrier film that (2) obtain stack gradually the electrode group that is wound into scroll, the electrode group that obtains is put into the battery case of an end opening, (solvent is an ethylene carbonate: diethyl carbonate=1: 1 (volume ratio), LiPF to inject electrolyte 3 grams
6Concentration be 1 rub/liter, make lithium ion battery A1 after the sealing No. 053450.
Embodiment 7
Different is that negative active core-shell material is G2 when negative pole prepares with embodiment 6.The battery note that makes is made A2.
Embodiment 8
Different is that negative active core-shell material is G3 when negative pole prepares with embodiment 6.The battery note that makes is made A3.
Embodiment 9
Different is that negative active core-shell material is G4 when negative pole prepares with embodiment 6.The battery note that makes is made A4.
Embodiment 10
Different is that negative active core-shell material is G5 when negative pole prepares with embodiment 6.The battery note that makes is made A5.
Comparative Examples 1
Take by weighing silica flour (particle diameter 5 μ m) 300g and aluminium powder 100g, send into planetary ball mill, it is 600 commentaries on classics/min that rotating speed is set, the powder that obtains mixing behind the ball milling 120min.With the powder 1000 ℃ of high-temperature process 180min under the Ar atmosphere protection that obtain, form silicon/aluminium alloy.
Take by weighing pitch 1Kg and be dissolved in the 5Kg oxolane, stir; With granularity is that the graphite powder 1Kg of 1-2 μ m slowly adds, and stirs gently and suitably grinds;
Above-mentioned silicon/aluminium alloy is added again, stir gently, at room temperature with solvent evaporates, the mixture that obtains moves in the sealed reaction system, adopts under the Ar atmosphere protection, handles 100min for 300 ℃.Obtain negative active core-shell material, the product note is made D1.
Comparative Examples 2
Different is that negative active core-shell material is D1 when negative pole prepares with embodiment 6.The battery note that makes is made H1.
Performance test
Reversible specific capacity and first charge-discharge efficiency first:
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, and the G1-G5 and D1, conductive carbon black and the Kynoar that are made by the foregoing description 1-5 and Comparative Examples 1 with 0.125 gram are positive electrode with 70: 10: 20 mixture of weight ratio, make button cell S1-S5 and J1.
Battery S1-S5 shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes, then respectively with 1 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt, after shelving 30 minutes, again with 0.5 milliampere, 0.3 milliampere, 0.1 milliampere, 0.06 milliampere, 0.03 milliampere constant current discharge to 0.005 volt, shelve after 30 minutes with 0.3 milliampere of electric current constant current charge, record charges to cell voltage and reaches 2.5 volts time, according to normal capacity (MAH)=charging current (milliampere) * charging interval of battery (hour) normal capacity of counting cell, normal capacity promptly gets the electrochemical specific capacity of battery cathode active material (G1-G5 and J1) divided by the weight of the negative active core-shell material (G1-G5 and J1) of battery, the ratio of electrochemical specific capacity and initial charge electrochemistry capacitance is the first charge-discharge efficiency of this material first, and the result is as shown in table 1.
The cycle performance test:
Under the room temperature, with battery (A1-A5 and H1) with 1C electric current constant current charge to 4.2V, then change constant voltage charging, cut-off current 0.05C; And then with battery with 1C electric current constant-current discharge to 3.1V.Repeat above step 100 time, obtain the capacity of 100 circulation backs of battery normal temperature 1C current discharge, battery capacity conservation rate after the computation cycles to 3.1V.The results are shown in Table 2.
Table 1
| Negative active core-shell material | ??G1 | ??G2 | ??G3 | ??G4 | ??G5 | ??D1 |
| Reversible specific capacity (mAh/g) first | ??900 | ??876 | ??702 | ??643 | ??625 | ??550 |
| First charge-discharge efficiency | ??91％ | ??85％ | ??82％ | ??74％ | ??68％ | ??66％ |
Table 2
| Battery | ??A1 | ??A2 | ??A3 | ??A4 | ??A5 | ??H1 |
| 100 circulation volume conservation rates | ??75％ | ??70％ | ??69％ | ??65％ | ??57％ | ??46％ |
From table 1, table 2 as can be seen, 100 circulation volume conservation rates of the lithium ion battery that G1-G5 makes also significantly improve, and the stable cycle performance of this explanation battery is good.Reversible specific capacity first and the first charge-discharge efficiency of the negative active core-shell material G1-G5 of embodiment all are significantly improved than the D1 of Comparative Examples simultaneously.
Claims (12)
1. negative active core-shell material that is used for lithium ion battery, it comprises dispersible carrier and is scattered in composite material in the dispersible carrier, and described dispersible carrier comprises silica fibre and carbon fiber, and described composite material is silicon/metal alloy.
2. negative active core-shell material according to claim 1 is characterized in that: the mass ratio of described carbon fiber and described silica fibre is 1: 1-1: 5.
3. negative active core-shell material according to claim 1 is characterized in that: the silicon in described silicon/metal alloy and the mol ratio of metal are 1: 1-1: 5.
4. negative active core-shell material according to claim 1 is characterized in that: the mass ratio of described dispersible carrier and described composite material is 1: 1-1: 10.
5. negative active core-shell material according to claim 1 is characterized in that: the metal in described silicon/metal alloy is a transition metal.
6. negative active core-shell material according to claim 5 is characterized in that: described transition metal be among Fe, Co, Ni, the Cu one or more.
7. negative active core-shell material according to claim 1 is characterized in that: the diameter of described silica fibre is 10-1000nm, and average length is 10nm～100 μ m; The diameter of described carbon fiber is 1～200nm, and average length is 10nm～100 μ m.
8. the preparation method of the described negative active core-shell material of claim 1, it may further comprise the steps:
(1) silica fibre, mixed being incorporated in of carbon fiber ball milling are protected high temperature sintering under the gas, obtain the silicon-carbon fiber; Silicon, metal ball milling mixed and under protection gas high temperature sintering, obtain silicon/metal alloy;
(2) silicon-carbon fiber and silicon/metal alloy are mixed, add in the dispersant, ultrasonic wave disperses to obtain slurry;
(3) with the volatilization of the dispersant in the slurry, K cryogenic treatment under protection gas.
9. preparation method according to claim 8 is characterized in that: the diameter of described silica fibre is 10-1000nm, and average length is 10nm～100 μ m; The diameter of described carbon fiber is 1～200nm, and average length is 10nm～100 μ m.
10. preparation method according to claim 8 is characterized in that: described protection gas is argon gas.
11. preparation method according to claim 8 is characterized in that: described dispersant is the N-methyl pyrrolidone.
12. lithium rechargeable battery, it comprises: battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises collector and the positive electrode active materials that loads on the collector, described negative pole comprises collector and the negative active core-shell material that loads on the collector, and described negative active core-shell material is any described negative active core-shell material of claim 1-7.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012068987A1 (en) * | 2010-11-25 | 2012-05-31 | Robert Bosch Gmbh | An electrode for lithium ion batteries and the method for manufacturing the same |
| CN105206818A (en) * | 2015-10-22 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of silicon/metal nano composite material |
| CN106207145A (en) * | 2016-09-26 | 2016-12-07 | 冯军 | A kind of silicium cathode active substance and preparation method thereof and the silene lithium battery prepared |
| CN110098404A (en) * | 2019-05-16 | 2019-08-06 | 四川大学 | Stair structure nano-structure porous silicon, its be sintered-etch preparation method and applications |
| CN115050925A (en) * | 2022-07-01 | 2022-09-13 | 山东仁丰特种材料股份有限公司 | Electrode material, preparation method, electrode plate and battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100835883B1 (en) * | 2006-07-14 | 2008-06-09 | 금호석유화학 주식회사 | Negative electrode material hybridizing carbon nanofiber for lithium ion secondary battery |
-
2008
- 2008-11-21 CN CN2008102178408A patent/CN101740766B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012068987A1 (en) * | 2010-11-25 | 2012-05-31 | Robert Bosch Gmbh | An electrode for lithium ion batteries and the method for manufacturing the same |
| CN105206818A (en) * | 2015-10-22 | 2015-12-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of silicon/metal nano composite material |
| CN105206818B (en) * | 2015-10-22 | 2017-12-01 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method and applications of silicon/metal nanometer composite material |
| CN106207145A (en) * | 2016-09-26 | 2016-12-07 | 冯军 | A kind of silicium cathode active substance and preparation method thereof and the silene lithium battery prepared |
| CN106207145B (en) * | 2016-09-26 | 2019-06-07 | 冯军 | A kind of silicium cathode active material and preparation method thereof and silene lithium battery obtained |
| CN110098404A (en) * | 2019-05-16 | 2019-08-06 | 四川大学 | Stair structure nano-structure porous silicon, its be sintered-etch preparation method and applications |
| CN115050925A (en) * | 2022-07-01 | 2022-09-13 | 山东仁丰特种材料股份有限公司 | Electrode material, preparation method, electrode plate and battery |
| CN115050925B (en) * | 2022-07-01 | 2023-09-01 | 山东仁丰特种材料股份有限公司 | Electrode material, preparation method, electrode plate and battery |
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|---|---|
| CN101740766B (en) | 2012-07-25 |
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