CN101188281A - Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material - Google Patents
Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material Download PDFInfo
- Publication number
- CN101188281A CN101188281A CNA2006101145944A CN200610114594A CN101188281A CN 101188281 A CN101188281 A CN 101188281A CN A2006101145944 A CNA2006101145944 A CN A2006101145944A CN 200610114594 A CN200610114594 A CN 200610114594A CN 101188281 A CN101188281 A CN 101188281A
- Authority
- CN
- China
- Prior art keywords
- particle
- porous
- silicon
- active core
- compound
- 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
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a negative electrode active material which is used in lithium ion secondary batteries, in particular to the material which uses silicon as a main component. The negative electrode active material is used to improve the size stability of the negative of the lithium ion secondary batteries in charging/discharging cycles and reduce the loss of irreversible electric capacity. The material comprises porous particles. The porous particle is of a compound matter which is formed by the connection of primary particles of the silicon and metal silicide. The porous particle has 10 to 60 percent of the internal porosity and 10 to 5000 nanometers of inner-pores.
Description
Technical field
The invention relates to a kind of negative active core-shell material that is used for lithium rechargeable battery, especially relevant a kind of with the negative active core-shell material of silicon as Main Ingredients and Appearance.
Background technology
Graphite is commercialization lithium rechargeable battery negative active core-shell material commonly used because have low, the low and smooth work low pressure of cost with excellent invertibity.Yet it is low theoretical capacitance relatively that graphite has, the shortcoming of about 370mAh/g (or 830Ah/L).
In seeking the process of the negative active core-shell material of high capacitance more, much making great efforts is on the material that concentrates on based on silicon.As the negative active core-shell material of lithium rechargeable battery, silicon has a theoretical capacitance greater than 3000mAh/g.But silicon can produce very big change in volume (greater than 300%) in charge, and silicon has poor electronic conductivity, make its on using by limited.Known negative pole with silicon thin film coating, it is to be formed by vacuum evaporation, can circulated by charge/discharge 300 above under the 3000mAh/g electric capacity, comprising micro-structural and the interface of film and base material or the film that use contains the alloy of amorphous silicon of this film of modification.Yet to do not have still so far that a kind of technology can success with the thick film granule electrode configuration of silicon utilization as traditional lithium rechargeable battery, most important reason is exactly that silicon mentioned above changes in the large volume of charge.
Summary of the invention
A main purpose of the present invention is to provide a kind of negative active core-shell material based on the lithium rechargeable battery of silicon of novelty.
Another object of the present invention is to provide a kind of preparation method of novelty based on the negative active core-shell material of the lithium rechargeable battery of silicon.
Another purpose of the present invention is to provide a kind of lithium rechargeable battery, and it has the negative active core-shell material based on silicon.
In order to realize the foregoing invention purpose, the present invention has disclosed a kind of complex particle of porous as this negative active core-shell material.This compound mainly is made up of silicon and metal silicide.The particle of this porous has the internal porosity (intra-particle porosity) of 10～60 volume % percentages and the particle inside aperture of 10～5000 nanometers.In the circulation that charging-discharging lithium ion embedding/embedding goes out, the complex particle of porous of the present invention shows obviously lower thickness swelling and capacitance fading rate compared to using the prepared negative pole of pure silicon particle.Above-mentioned improvement has mainly partly been held the volumetric expansion that the silicon lithium alloyage is produced owing to the inside aperture that presets of complex particle of the present invention.
Execution mode
The present invention discloses a kind of negative active core-shell material that is used for lithium rechargeable battery, the particle that comprises porous, the compound offspring that the particle of this porous links for the primary particle of littler Si primary particle and metal silicide, and internal porosity and aperture that the particle of this porous has 10～60 volume % are the inside aperture of 10～5000 nanometers, are preferable with about 200 nanometers.
If the internal porosity of this porous granule then can't reach significant electrode stablizing effect less than 10%.If greater than 60%, then the volumetric capacitance amount of particle is too low, and reduces economic use value.
Preferable, the particle of this porous has 30～60% internal porosity and 0.1～100 micron particle diameter, and this metal is to be selected from one of nickel, iron, copper, cobalt, tungsten, titanium or its combination.
Preferable, the particle of this porous is the compound of silicon and nickle silicide (NiSi).
Preferable, the mol ratio that this porous granule comprises silicon and metal silicide is 1: 0.5 to 1: 10.If the content of metal silicide is lower than mol ratio=1: 0.5 content, then can't reach satisfied electrode stablizing effect.If the content of metal silicide is higher than mol ratio=1: 10 content, then the capacitance of complex particle is too low, and does not have economic use value.The mol ratio of Si and metal silicide, with 1: 1～1: 2 for better.
Preferable, form the silicon of this compound and the primary particle particle diameter of metal silicide and be not more than 5 microns, better to be not more than 2 microns.When the particle diameter of primary particle is healed their distribution of little expression more evenly.
Preferable, about 40～50 volume % of the internal porosity of the porous granule of this compound.
The method of a kind of suitable preparation negative active core-shell material of the present invention, comprise silicon particle reaction thing is ground under an inert atmosphere with the metallic reactant, to form metal silicide: will grind resulting product and be dipped in the acid, unreacted metal is dissolved in this acid solution; Obtain the complex particle of porous by the means of Separation of Solid and Liquid; Clean the residual acid on the complex particle of this porous and the complex particle of dry porous of cleaning.
Preferable, this silicon particle reaction thing has 0.1～100 micron particle diameter, and this metallic reactant has 0.1～100 micron particle diameter.Better, the particle diameter of this silicon particle reaction thing approximates the particle diameter of this metallic reactant.
Preferable, this metal silicide and silicon particle reaction thing are insoluble to this acid in fact.
The present invention also discloses a kind of lithium rechargeable battery, comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And an electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this negative pole comprises a colleeting comb (current collector) base material; Reach a lip-deep negative active core-shell material attached to this base material; It is characterized in that this negative active core-shell material comprises the particle of porous, and the compound offspring that links for the primary particle of littler silicon primary particle and metal silicide of the particle of this porous, and the particle of this porous has the internal porosity of 10～60 volume %, and the hole aperture is the inside aperture of 10～5000 nanometers.
Preferable, the particle of this porous has the internal porosity of 30～60 volume % and 0.1～100 micron particle diameter, and wherein this metal is to be selected from one of nickel, iron, copper, cobalt, tungsten, titanium or its combination.
Preferable, the particle of this porous is the compound of silicon and nickle silicide.
Preferable, the silicon of this compound and the mol ratio of metal silicide are 1: 0.5 to 1: 10, are better with about 1: 1～1: 2.
Preferable, the particle diameter of forming the primary particle of the silicon of this compound and metal silicide is not more than 5 microns, and is better to be not more than 2 microns.
Preferable, about 30～60 volume % of the internal porosity of this compound are better person with 40～50 volume %.
Preferable, about 200 nanometers in the aperture of the inside aperture that the particle of this porous has.
Description of drawings
Fig. 1 for ball milling in the embodiment of the invention after resulting combination product powder (collection of illustrative plates (a)) and the X-ray diffraction collection of illustrative plates of (collection of illustrative plates (b)) afterwards before utilizing acid solution to corrode to handle.
Fig. 2 is for being linked scanning electron microscope (SEM) photo of the porous compound offspring of the present invention that combines by littler silicon primary particle and nickle silicide primary particle in the embodiment of the invention.
Fig. 3 shows the hole analysis result of complex particle of the present invention, and wherein solid line and data point are the pore-size distribution that utilizes the mercury apertometer to measure; Dotted line is the particle interior (than aperture) and outer (than macropore) hole distribution curve of particle that utilizes Gaussian distribution curve to decomposite.
Fig. 4 is a charge and discharge cycles test result of utilizing the prepared negative pole of pure silicon particle and complex particle of the present invention, shows the relation of residual capacity and cycle-index.
Embodiment
Embodiment:
Highly purified element state powder silicon (99% ,-325 meshes, Aldrich company) and nickel (5 μ m, CERAC company) added give the mechanical type alloying and synthesize alloy powder, wherein the consumption mol ratio of silicon and nickel is 1: 2.The mechanical type alloying is used delegation's celestial body grinding machine (planetary mill) (Fritsch company, model Pulverisette P7) and stainless steel ball grinder and ball under argon (Ar) atmosphere, carry out, wherein the weight ratio of ball and powder is 14: 1, and the stearic acid [CH of 0.5 weight %
3(CH
2)
16COOH] be used as lubricant and add.With the 400rpm abrasive dust after 16 hours, an intermediate product contains nickel, silicon, is formed with the composite material of nickle silicide.The product that abrasive dust is obtained places 0.5M aqueous solution of nitric acid 1 hour to eat away nickel.(inductively coupled plasma, ICP) frequency spectrograph (spectroscopy) (Optima company, model 3000XL) adds the prediction amount with inductance coupling formula electricity slurry to be dissolved in nickel amount in this aqueous solution of nitric acid.From this aqueous solution of nitric acid, isolate powder at last, with water clean and in vacuum furnace with 50 ℃ of dryings 6 hours, so obtain the compound offspring of silicon and nickle silicide binding.
The negative pole coating composition is by the silicon and the nickle silicide complex particle of the above-mentioned preparation of 62 weight %, and the adhesive (binder) of the conductive additive of 30 weight % and 8 weight % is formed, and wherein this percentage by weight is the dry weight based on composition.This adhesive is styrene butadiene rubbers (styrene-butadienerubber, SBR) (Asahi Chemicals company, code name L1571) and sodium-carbonyl-methylcellulose (sodium-carboxyl-methylcellulose, SCMC) (DKS International company, code name WS-C Collogen) is formed with 1: 1 weight ratio.This conductive additive is made up of with 5: 1 weight ratios graphite flake (graphite flakes) (TIMCAL company, code name KS6) and nanometer carbon black (TIMCAL company, code name Super P, 40 nanometers).This negative pole coating composition and deionized water obtain a slurry with weight ratio mixing in 1: 2.This slurry is coated on two surfaces of a Copper Foil, roll and dry solvent after to obtain gross thickness be 64 microns negative pole, wherein copper thickness is 14 microns.
CR2032 coin shape battery is assembled to carry out the electrochemical properties analysis.Negative pole uses the negative pole of above-mentioned preparation and in the same way but replace silicon and the prepared person of nickle silicide compound with pure silicon respectively.Lithium paper tinsel just very.(ethylene carbonate is EC) with Methylethyl carbonic ester (methyl ethyl carbonate, MEC) the 1.0M LiPF in 1: 2 the mixed liquor of volume ratio in order to be dissolved in vinyl carbonate for electrolyte
6Unless the voltage of following indication specializes is with respect to this Li positive pole.
The charge/discharge test is to adopt constant-current constant-voltage (CC-CV) pattern to carry out between voltage range 0.001 to 1.2V.Should decide the electric current of deciding that the electric current process is used 0.1mA/mg; Should decide voltage course use 0.001V decide a voltage and a cut-off current 0.03A/g.The X-ray diffractometer is to use Mac-Science/MXP diffractometer and CuK α radiation to carry out.Grain diameter measurement is to be undertaken by light-scattering analysis.Porosity and pore size distribution are to use the mercury apertometer to carry out.
About 20 microns of the average grain diameter of Si powder, particle diameter accounts for about 77% (volume ratio) between 10 to 40 microns powder.Mixed-powder went to corrode with dilute nitric acid solution again behind the ball milling through 16 hours and dissolves the not nickel of alloying, and this purpose that corrodes program is the porosity that increases powder integral body.Fig. 1 demonstrates sample at the X-ray diffraction collection of illustrative plates through erosion program front and back, only surplus nickle silicide (NiSi) of end product and silicon.Consider the dissolved amount of nickel, the weight ratio that gets nickle silicide and silicon as calculated is about 76/24 (the about 1.0/1.0 of mol ratio).The result is the particle size distribution of a broadness via its granularmetric analysis of the powder after the erosion program, greater than its particle diameter of powder of 90% percent by volume between 2～10 microns.As shown in Figure 2, sweep electron microscope and X-ray energy spectrometer show that this experiment serves as reasons less than a porousness framework of 2.0 microns silicon and nickle silicide composition that primary particle links via the prepared compound offspring of ball milling and erosion program.Fig. 3 is the analysis result that the hole of this complex particle distributes, and this is distributed with two peaks, respectively in 200 nanometers and 600 nanometers, is a typical bimodal distribution curve.For a porous material, mainly to contribute than the peak (600 nanometer) of macroscopic void owing to particle and interparticle space, it depends on the tightness of filling powder when measuring, and is not the character of particle itself.On the contrary, then provided by the particle inside holes than the peak (200 nanometer) of small holes, its distribution of sizes scope is consistent with the viewed result of sweep electron microscope.In theory can Gaussian Profile these two peak separate computations be obtained whole pore volumes of the inner holes of particle, through so being calculated as about 0.151cc/g.Consider that the solid density of silicon and nickle silicide gets the solid volume 0.238cc/g of this complex particle,
It is 38.9% that particle internal porosity=(particle internal pore volume)/(solid volume of particle internal pore volume+particle) can calculate its particle internal porosity.
The cycle life testing capacitor amount result of the negative electrode of the siliceous and nickle silicide complex particle of pure silicon electrode and processing procedure of the present invention as shown in Figure 4.For the pure silicon negative material, charging (lithium is moved into) capacitance can reach about 3300mAh/g under the condition of electric current 0.1A/g for the first time, but the irreversible loss of capacitance up to 62% is arranged in discharge (lithium is moved out) process, only through five cycle-indexes, the charging capacitor amount fails rapidly to about 200mAh/g; The electrode of reviewing by complex particle combination shows good cyclical stability under the identical condition that discharges and recharges, the charging capacitor amount of first lap is 1250mAh/g, the capacitance performance of still possessing 540mAh/g after 50 times discharge and recharge.
Cross-section structure to the electrode after the charge is observed.The preparation of sample is to carry out in the glove box of argon inflation.Before analysis, the electrode after this circulation in glove box by with diethyl carbonate (diethyl carbonate, DEC) rinse and drying.Find that by scanning microscopic examination the thickness of pure silicon electrode and complex particle electrode is respectively 55 and 45 microns without before the charge-discharge test.After discharging and recharging through 10 times, the pure silicon electrode expand into 200 microns, and the complex particle electrode only expand into 96 microns, shows to use complex particle can reduce the change in volume of electrode layer when discharging and recharging, and improves the stability of charge and discharge cycles.
Apparently, select the metal that can form alloy for use with Si, for example, metals such as nickel, copper, iron, cobalt, tungsten, titanium, by high-energy ball-milling process and erosion program, all can prepare complex particle negative material,, reduce the effect of capacitance decay to reach the stability of similar enhancement charge and discharge cycles with porosity characteristic.
The theoretical weight capacitance of the complex particle of embodiment is 1298mAh/g, and the solid density of considering this composite material is 4.35g/cm
3, the theoretical volume capacitance that composite material provided that can calculate this porosity 40% is 3389mAh/cm
3And present stage business-like graphite cathode compare, theoretical weight capacitance and volume capacitance are respectively 372mAh/g and 838mAh/cm
3, this porousness complex particle shows its advantage fully.
Claims (29)
1. a lithium rechargeable battery comprises a positive pole; One negative pole; It separates this positive pole and negative pole one barrier film; And an electrolyte its form a lithium ion passage between this positive pole and the negative pole, wherein this negative pole comprises a colleeting comb base material; Reach a lip-deep negative active core-shell material attached to this base material; It is characterized in that this negative active core-shell material comprises the particle of porous, and the compound offspring that links for littler silicon primary particle and metal silicide primary particle of the particle of this porous, wherein the particle of this porous has the particle internal porosity of 0.1～100 micron particle diameter and 10～60 volume %.
2. lithium rechargeable battery as claimed in claim 1, wherein the particle of this porous has the particle inside aperture of 10～5000 nanometer sizes.
3. lithium rechargeable battery as claimed in claim 1 or 2, wherein this metal is to be selected from nickel, iron, copper, cobalt, tungsten, titanium or its combination.
4. lithium rechargeable battery as claimed in claim 3, wherein the particle of this porous is the compound offspring of silicon and nickle silicide.
5. lithium rechargeable battery as claimed in claim 1 or 2, wherein the particle diameter of silicon primary particle and metal silicide primary particle is not more than 2 microns.
6. lithium rechargeable battery as claimed in claim 1 or 2, wherein the mol ratio of the silicon of this compound and metal silicide is 1: 0.5 to 1: 10.
7. lithium rechargeable battery as claimed in claim 6, wherein the silicon that comprises of this compound and the mol ratio of metal silicide are 1: 1.
8. lithium rechargeable battery as claimed in claim 1 or 2, wherein internal porosity 40～50 volume % of this porous granule.
9. lithium rechargeable battery as claimed in claim 1 or 2, wherein the particle of this porous has the particle inside aperture of 200 nanometer sizes.
10. negative active core-shell material that is used for lithium rechargeable battery, the particle that comprises porous, the compound offspring that the particle of this porous links for littler silicon primary particle and metal silicide primary particle, the particle of this porous has the particle internal porosity of 0.1～100 micron particle diameter and 10～60 volume %.
11. negative active core-shell material as claimed in claim 10, wherein the particle of this porous has the particle inside aperture of 10～5000 nanometer sizes.
12. as claim 10 or 11 described negative active core-shell materials, wherein this metal is to be selected from nickel, iron, copper, cobalt, tungsten, titanium or its combination.
13. negative active core-shell material as claimed in claim 12, wherein the particle of this porous is the compound of silicon and nickle silicide.
14. as claim 10 or 11 described negative active core-shell materials, the silicon primary particle wherein and the particle diameter of metal silicide primary particle are not more than 2 microns.
15. as claim 10 or 11 described negative active core-shell materials, wherein the mol ratio of the silicon of this compound and metal silicide is 1: 0.5 to 1: 10.
16. negative active core-shell material as claimed in claim 15, wherein the mol ratio of the silicon of this compound and metal silicide is 1: 1.
17. as claim 10 or 11 described negative active core-shell materials,, wherein the internal porosity of this porous granule is 40～50 volume %.
18. as claim 10 or 11 described negative active core-shell materials, wherein the particle of this porous has the particle inside aperture of 200 nanometer sizes.
19. method for preparing negative active core-shell material as claimed in claim 10, comprise silicon particle reaction thing is ground under an inert atmosphere with the metallic reactant, to form metal silicide: will grind resulting product and be dipped in the acid, unreacted metal is dissolved in this acid; From this acid, obtain the complex particle of porous by the means of Separation of Solid and Liquid; Clean the residual acid on the complex particle of this porous and the complex particle of dry porous of cleaning.
20. method as claimed in claim 19, wherein this silicon particle reaction thing has 0.1～100 micron particle diameter, and this metallic reactant has 0.1～100 micron particle diameter.
21. method as claimed in claim 19, wherein the particle diameter of this silicon particle reaction thing approximates the particle diameter of this metallic reactant.
22. method as claimed in claim 19, wherein this metal silicide and silicon particle reaction thing are insoluble to this acid in fact.
23. method as claimed in claim 19, wherein the complex particle of this porous has the particle inside aperture of 10～5000 nanometer sizes.
24. method as claimed in claim 23, wherein size 200 nanometers of this inside aperture.
25. method as claimed in claim 19, wherein this metallic reactant is to be selected from nickel, iron, copper, cobalt, tungsten, titanium or its combination.
26. method as claimed in claim 25, wherein the complex particle of this porous is the compound of silicon and nickle silicide.
27. method as claimed in claim 26, wherein the mol ratio of the silicon of this compound and metal silicide is 1: 0.5 to 1: 10.
28. method as claimed in claim 27, wherein the mol ratio of the silicon of this compound and metal silicide is 1: 1.
29. method as claimed in claim 19, wherein the complex particle of this porous has the internal porosity of 40～50 volume %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101145944A CN101188281A (en) | 2006-11-16 | 2006-11-16 | Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101145944A CN101188281A (en) | 2006-11-16 | 2006-11-16 | Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101188281A true CN101188281A (en) | 2008-05-28 |
Family
ID=39480551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101145944A Pending CN101188281A (en) | 2006-11-16 | 2006-11-16 | Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101188281A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102263231A (en) * | 2010-05-28 | 2011-11-30 | 株式会社日立制作所 | Anode for nonaqueous secondary battery and nonaqueous secondary battery |
| CN102916167A (en) * | 2011-08-04 | 2013-02-06 | 上海交通大学 | Mesoporous silicon composite utilized as lithium ion battery cathode material and preparing method thereof |
| CN103201060A (en) * | 2010-11-08 | 2013-07-10 | 古河电气工业株式会社 | Nanoscale particles used in negative electrode for lithium ion secondary battery and method for manufacturing same |
| WO2014032407A1 (en) * | 2012-08-28 | 2014-03-06 | 华为技术有限公司 | Silicon negative electrode pole piece of lithium ion battery and preparation method thereof, and lithium ion battery |
| CN104125927A (en) * | 2012-03-21 | 2014-10-29 | 古河电气工业株式会社 | Porous silicon particles and porous silicon-composite particles |
| GB2529410A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| GB2529411A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| US10008716B2 (en) | 2012-11-02 | 2018-06-26 | Nexeon Limited | Device and method of forming a device |
| US10077506B2 (en) | 2011-06-24 | 2018-09-18 | Nexeon Limited | Structured particles |
| US10090513B2 (en) | 2012-06-01 | 2018-10-02 | Nexeon Limited | Method of forming silicon |
| US10103379B2 (en) | 2012-02-28 | 2018-10-16 | Nexeon Limited | Structured silicon particles |
| US10388948B2 (en) | 2012-01-30 | 2019-08-20 | Nexeon Limited | Composition of SI/C electro active material |
| US10396355B2 (en) | 2014-04-09 | 2019-08-27 | Nexeon Ltd. | Negative electrode active material for secondary battery and method for manufacturing same |
| US10476072B2 (en) | 2014-12-12 | 2019-11-12 | Nexeon Limited | Electrodes for metal-ion batteries |
| US10522824B2 (en) | 2014-07-23 | 2019-12-31 | Nexeon Ltd | Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles |
| US10586976B2 (en) | 2014-04-22 | 2020-03-10 | Nexeon Ltd | Negative electrode active material and lithium secondary battery comprising same |
| CN113383450A (en) * | 2019-02-08 | 2021-09-10 | 三洋电机株式会社 | Cylindrical battery |
| US11127945B2 (en) | 2016-06-14 | 2021-09-21 | Nexeon Limited | Electrodes for metal-ion batteries |
-
2006
- 2006-11-16 CN CNA2006101145944A patent/CN101188281A/en active Pending
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8895186B2 (en) | 2010-05-28 | 2014-11-25 | Hitachi, Ltd. | Anode for lithium-ion rechargeable battery and lithium-ion rechargeable battery including same |
| CN102263231A (en) * | 2010-05-28 | 2011-11-30 | 株式会社日立制作所 | Anode for nonaqueous secondary battery and nonaqueous secondary battery |
| CN103201060A (en) * | 2010-11-08 | 2013-07-10 | 古河电气工业株式会社 | Nanoscale particles used in negative electrode for lithium ion secondary battery and method for manufacturing same |
| US10822713B2 (en) | 2011-06-24 | 2020-11-03 | Nexeon Limited | Structured particles |
| US10077506B2 (en) | 2011-06-24 | 2018-09-18 | Nexeon Limited | Structured particles |
| US9748573B2 (en) | 2011-08-04 | 2017-08-29 | Robert Bosch Gmbh | Mesoporous silicon compound used as lithium-ion cell negative electrode material and preparation method thereof |
| CN102916167A (en) * | 2011-08-04 | 2013-02-06 | 上海交通大学 | Mesoporous silicon composite utilized as lithium ion battery cathode material and preparing method thereof |
| CN102916167B (en) * | 2011-08-04 | 2016-08-03 | 上海交通大学 | Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof |
| US10388948B2 (en) | 2012-01-30 | 2019-08-20 | Nexeon Limited | Composition of SI/C electro active material |
| US10103379B2 (en) | 2012-02-28 | 2018-10-16 | Nexeon Limited | Structured silicon particles |
| CN104125927B (en) * | 2012-03-21 | 2016-05-25 | 古河电气工业株式会社 | Porous silicon particle and Porous silicon complex particles |
| CN104125927A (en) * | 2012-03-21 | 2014-10-29 | 古河电气工业株式会社 | Porous silicon particles and porous silicon-composite particles |
| US10090513B2 (en) | 2012-06-01 | 2018-10-02 | Nexeon Limited | Method of forming silicon |
| WO2014032407A1 (en) * | 2012-08-28 | 2014-03-06 | 华为技术有限公司 | Silicon negative electrode pole piece of lithium ion battery and preparation method thereof, and lithium ion battery |
| US10008716B2 (en) | 2012-11-02 | 2018-06-26 | Nexeon Limited | Device and method of forming a device |
| US10396355B2 (en) | 2014-04-09 | 2019-08-27 | Nexeon Ltd. | Negative electrode active material for secondary battery and method for manufacturing same |
| US10693134B2 (en) | 2014-04-09 | 2020-06-23 | Nexeon Ltd. | Negative electrode active material for secondary battery and method for manufacturing same |
| US10586976B2 (en) | 2014-04-22 | 2020-03-10 | Nexeon Ltd | Negative electrode active material and lithium secondary battery comprising same |
| US11196042B2 (en) | 2014-07-23 | 2021-12-07 | Nexeon Ltd | Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles |
| US10522824B2 (en) | 2014-07-23 | 2019-12-31 | Nexeon Ltd | Method for preparing silicon-based active material particles for secondary battery and silicon-based active material particles |
| GB2529410A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| EP3183765A1 (en) * | 2014-08-18 | 2017-06-28 | Nexeon Limited | Electroactive materials for metal-ion batteries |
| GB2529411A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| US10476072B2 (en) | 2014-12-12 | 2019-11-12 | Nexeon Limited | Electrodes for metal-ion batteries |
| US11127945B2 (en) | 2016-06-14 | 2021-09-21 | Nexeon Limited | Electrodes for metal-ion batteries |
| CN113383450A (en) * | 2019-02-08 | 2021-09-10 | 三洋电机株式会社 | Cylindrical battery |
| CN113383450B (en) * | 2019-02-08 | 2024-06-18 | 松下新能源株式会社 | Cylindrical battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101188281A (en) | Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material | |
| Zhang et al. | Harnessing the concurrent reaction dynamics in active Si and Ge to achieve high performance lithium-ion batteries | |
| Song et al. | Yolk-shell structured Sb@ C anodes for high energy Na-ion batteries | |
| Liu et al. | Three-dimensionally interconnected nickel–antimony intermetallic hollow nanospheres as anode material for high-rate sodium-ion batteries | |
| CN100477372C (en) | Secondary battery | |
| Wu et al. | Three-dimensionally porous Fe3O4 as high-performance anode materials for lithium–ion batteries | |
| Liu et al. | Preparation and electrochemical properties of Fe-Sn (C) nanocomposites as anode for lithium-ion batteries | |
| CN101640261A (en) | Cathode of lithium-ion secondary battery, preparation method and lithium-ion secondary battery | |
| Lyu et al. | Improving the cycling performance of silver-zinc battery by introducing PEG-200 as electrolyte additive | |
| Osaka et al. | New Si–O–C composite film anode materials for LIB by electrodeposition | |
| CN105932284B (en) | A kind of close cladded type composite material and preparation method of mesoporous carbon and application | |
| Chen et al. | Facile synthesis and stable lithium storage performances of Sn-sandwiched nanoparticles as a high capacity anode material for rechargeable Li batteries | |
| Du et al. | Structure and electrochemical properties of ball-milled Co-carbon nanotube composites as negative electrode material of alkaline rechargeable batteries | |
| CN107946581A (en) | A kind of power-type sodium-ion battery positive material and preparation method thereof | |
| CN102569794A (en) | Carbon-coating method for lithium iron phosphate anode material | |
| Hu et al. | Current Progress of Anode‐Free Rechargeable Sodium Metal Batteries: Origin, Challenges, Strategies, and Perspectives | |
| CN106558689A (en) | A kind of electrochemical in-situ method prepares the method for two-arch tunnel hybrid metal selenides and its application | |
| Liu et al. | Progress of metal-phosphide electrodes for advanced sodium-ion batteries | |
| Liu et al. | Binder-free integration of insoluble cubic CuCl nanoparticles with a homologous Cu substrate for lithium ion batteries | |
| Zhang et al. | Fabrication and electrochemical performance of Sn–Ni–Cu alloy films anode for lithium-ion batteries | |
| Lu et al. | Superior Fast‐Charging Lithium‐Ion Batteries Enabled by the High‐Speed Solid‐State Lithium Transport of an Intermetallic Cu6Sn5 Network | |
| CN102054961A (en) | Active negative pole piece and preparation method thereof | |
| Chen et al. | Pb-sandwiched nanoparticles as anode material for lithium-ion batteries | |
| Wang et al. | Boosting the cycling stability of LixSi alloy microparticles through electroless copper deposition | |
| CN106876684A (en) | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080528 |