CN104701502A - Lithium ion battery cathode material and preparation method thereof, and lithium ion battery - Google Patents
Lithium ion battery cathode material and preparation method thereof, and lithium ion battery Download PDFInfo
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- CN104701502A CN104701502A CN201310652472.0A CN201310652472A CN104701502A CN 104701502 A CN104701502 A CN 104701502A CN 201310652472 A CN201310652472 A CN 201310652472A CN 104701502 A CN104701502 A CN 104701502A
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- lithium ion
- ion battery
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- battery negative
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 103
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010406 cathode material Substances 0.000 title abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 141
- 239000000463 material Substances 0.000 claims abstract description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 claims abstract description 29
- 239000010931 gold Substances 0.000 claims abstract description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 239000004332 silver Substances 0.000 claims abstract description 18
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 92
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 38
- 239000000725 suspension Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000005253 cladding Methods 0.000 claims description 16
- -1 gold ion Chemical class 0.000 claims description 14
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000479 mixture part Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 172
- 239000010703 silicon Substances 0.000 abstract description 99
- 239000000377 silicon dioxide Substances 0.000 abstract description 86
- 229910052710 silicon Inorganic materials 0.000 abstract description 59
- 239000002131 composite material Substances 0.000 abstract description 57
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- MSVOWLCCSIJLAG-UHFFFAOYSA-N [Si]=O.[Si]=O Chemical compound [Si]=O.[Si]=O MSVOWLCCSIJLAG-UHFFFAOYSA-N 0.000 abstract 1
- 238000007323 disproportionation reaction Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 89
- 235000012239 silicon dioxide Nutrition 0.000 description 66
- 229910052814 silicon oxide Inorganic materials 0.000 description 40
- 238000000498 ball milling Methods 0.000 description 24
- 239000012298 atmosphere Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000011049 pearl Substances 0.000 description 12
- 239000010439 graphite Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000003376 silicon Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 4
- NTVYFDOMBHOLGP-UHFFFAOYSA-N gold nitric acid Chemical compound [Au].O[N+]([O-])=O NTVYFDOMBHOLGP-UHFFFAOYSA-N 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000009829 pitch coating Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method, and a lithium ion battery. A structure of the lithium ion battery cathode material is characterized in that a first mixture obtained by disproportionation of silicon oxide silicon monoxide is coated by one or more from silver, gold and platinum, the first mixture mainly comprises a composite material of silicon and silica, and the composite material of silicon and silica is a matrix material of the lithium ion battery cathode material. Metal silver, gold and platinum have good conductivity and are stable in air, and the conductivity can not be reduced due to oxidation. A conductive frame is formed by coating one or more of metal silver, gold and platinum on the first mixture for convenient electron transmission, problem of no conductivity of silicon in the first mixture and silica in the silica composite material can be made up, the lithium ion battery cathode material has good conductivity, so that cycle life as well as charge and discharge efficiency of the lithium ion battery made by the material can be increased.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery cathode material and its preparation method, lithium ion battery.
Background technology
At present, the lithium ion battery of production and application mainly adopts graphite negative electrodes material, but the embedding lithium capacity of the theory of graphite is 372mAh/g, and reality reaches 370mAh/g, therefore, graphite negative electrodes material on capacity almost without room for promotion.
The nearly more than ten years, various novel high power capacity and high magnification negative material are developed, wherein silica-base material becomes study hotspot due to its high specific discharge capacity (theoretical specific capacity of silicon is 4200mAh/g), but this material in doff lithium process along with serious volumetric expansion and contraction, cause the electroactive material powder of detached on electrode, finally cause capacity attenuation.In order to overcome the special capacity fade of silicon based anode material, generally that silicon and other inactive metals (as Fe, Al, Cu etc.) are formed alloy, as Chinese patent CN03116070.0 discloses silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and preparation method thereof; Or homogenize material is distributed in other active or non-active materials and forms composite material (as Si-C, Si-TiN etc.), as Chinese patent CN02112180.X discloses Si-C composite material and the preparation method of used as negative electrode of Li-ion battery height ratio capacity.More conventional method is the Surface coating one deck amorphous carbon at silicon nanoparticle, as CN200910027938.1 discloses the composite negative pole material of a kind of half fluidised form pitch-coating nano-silicon and graphite; CN200910037666.3 discloses a kind of preparation method of composite negative pole material of pitch-coating nano-silicon.
Although said method has done certain modification for silicium cathode material, above-mentioned silicium cathode material electrochemical performance is still undesirable.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of lithium ion battery cathode material and its preparation method, lithium ion battery are provided, one or more first mixtures obtained after silicon monoxide disproportionated reaction in this negative material in argentiferous, gold, platinum form conducting matrix grain outward, are convenient to electric transmission.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of lithium ion battery negative material, and its structure is one or more that the first mixture obtained after silicon monoxide disproportionated reaction is coated with in silver, gold, platinum.
Preferably, the particle diameter of described silicon monoxide is 1000 ~ 15000 orders.
Preferably, the gross mass of one or more of the silver of described first mixture outer cladding, gold, platinum accounts for 0.5 ~ 30% of described lithium ion battery negative material quality.
Preferably, described second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide, find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale (1nm ~ 50nm), silicon accounts for 25 ~ 33% of the second mixture quality, and silicon dioxide accounts for 50 ~ 67% of the second mixture quality.
The present invention also provides a kind of preparation method of above-mentioned lithium ion battery negative material, comprises the following steps:
(1) the second mixture is obtained after silicon monoxide generation disproportionated reaction;
(2) one or more in silver salt, golden salt, platinum salt and described second mixture are added to the water obtain suspension, add hydrofluoric acid again, described second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material of one or more that is coated with at this first mixture in silver, gold, platinum.
Preferably, step is also comprised (i) between described step (1) and described step (2): described second mixture being worn into particle diameter is 1000 ~ 15000 object particles.
Preferably, described in described step (1), the temperature of silicon monoxide disproportionated reaction is 700 ~ 1200 DEG C, and the time is 0.5 ~ 24 hour.
Preferably, the addition of hydrofluoric acid described in described step (2) adds the hydrofluoric acid of the 5 ~ 15wt% of 10 ~ 40g according to every gram of metal ion in the described suspension of correspondence.Directly limit the amount of hydrofluoric acid according to the amount of metal ion, when metal ion and SiO react, hydrofluoric acid is all enough, but the amount of hydrofluoric acid is much smaller than SiO in the second mixture
2the amount of whole removing.Here hydrofluoric acid just plays a booster action, and the reproducibility of SiO is brought into play.
Preferably, the total concentration of one or more in the silver ion in suspension described in described step (2), gold ion, platinum ion is 0.0001 ~ 0.01mol/L.
Preferably, described in described step (2), described in suspension, the amount of the second mixture is 5 ~ 30g/ml.
The present invention also provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present invention is one or more that the first mixture obtained after silicon monoxide disproportionated reaction is coated with in silver, gold, platinum, first mixture mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.Argent, gold, platinum conductivity are better, and enough stable in atmosphere, can not reduce its conductivity because of oxidation.One or more in the argent of the first mixture outer cladding, gold, platinum define conducting matrix grain, be convenient to electric transmission, the silicon dioxide that compensate in the composite material of silicon in the first mixture and silicon dioxide does not have the problem of conductivity, make this lithium ion battery negative material have good conductivity, thus improve cycle life and the efficiency for charge-discharge of the lithium ion battery using this material to make.
The conductivity of silver, gold, platinum far above amorphous carbon, graphite etc., and is rich in ductility, can stretch accordingly along with the change in volume of the active material particle in the first mixture in the negative material in lithium ion battery charge and discharge process or shrink.Therefore, in the first mixture outer cladding silver, gold, one or more in platinum, lithium ion battery negative material conductivity can effectively be increased on the one hand; On the other hand due to the ductility of metal material, the stability of this structure under change in volume can be kept, be conducive to the cycle life extending ion cathode material lithium.
The raw material that in the present invention, the preparation method of lithium ion battery negative material uses is easy to get, preparation method's technique is simple.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 2000 orders) is placed in crucible; and put into atmosphere furnace; 800 DEG C are warmed up under the protection of argon gas atmosphere; heat 24 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 8nm, and silicon accounts for 32% of the first mixture quality, and silicon dioxide accounts for 64% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 5000 object particles this second mixture ball milling.
(3) be added to the water by above-mentioned second mixture, then add appropriate liquor argenti nitratis ophthalmicus, obtain suspension, wherein, in this suspension, the amount of the second mixture is 10g/ml, and the concentration of the silver ion in suspension is 0.01mol/L.Then at 30W/cm
2ultrasonication under the ultrasonic condition of the sound intensity, the second mixture is made fully to disperse and mix with liquor argenti nitratis ophthalmicus, stir the hydrofluoric acid solution that lower dropping is enough, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 5wt% of 10g according to every gram of silver ion in the described suspension of correspondence, silver ion reacts according to following equation, M in equation
n+for Ag
+, certain M also can represent gold or platinum.
M
n++0.5nSiO+3nHF→M↓+0.5nH
2SiF
6+0.5nH
2O+nH
+
Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with argent at this first mixture.Wherein, the quality of the argent of the first mixture outer cladding accounts for 0.5% of the quality of lithium ion battery negative material.
By the preparation method in this enforcement, silver in the first mixture outer cladding obtained after silicon monoxide disproportionated reaction, this preparation method relative to direct by the first mixture after silicon monoxide disproportionated reaction directly with carry out calcination after argent dry mixed again and prepare compared with lithium ion battery negative material, the preparation method in the present embodiment is more even at the first mixture outer cladding silver.And owing to being by the directly sub-pasc reaction with the oxidation in the second mixture of the silver ion in solution at the chemical reaction of the first mixture outer cladding silver in the present embodiment, the contact-making surface of both reactions is exactly the outer surface of the sub-silicon of oxidation in the second mixture, so the silver generated after reaction is also at the outer surface of former second mixture, and close contact, the first mixture is become, so namely silver is closely coated on the outer surface of the first mixture due to after the partial reaction that the sub-silicon of the oxidation in the second mixture occurs.
Gained lithium ion battery negative material is mixed according to mass ratio 80: 10: 10 with conductive agent acetylene black, binding agent PVDF respectively, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF6 solution of 1mol/L, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1), barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
The charge-discharge performance test of the button cell that lithium ion battery negative material prepared by the present embodiment is made: first discharge specific capacity is 1556mAh/g, the specific discharge capacity after 100 times that circulates is 809mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is that the first mixture obtained after silicon monoxide disproportionated reaction is coated with silver, first mixture mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.The composite material of this silicon and silicon dioxide is generated through high temperature disproportionated reaction by silicon monoxide, and silicon is wherein nano-silicon.In the composite material of silicon and silicon dioxide, silicon accounts for the quality of about 1/3rd, and silicon dioxide accounts for the quality of about 2/3rds.In the composite material of silicon and silicon dioxide, in silica, in doff lithium process, the silicon dioxide in the composite material of silicon and silicon dioxide can stop silicon grain in repeatedly doff lithium process, electrochemistry sintering occur and reunite in silicon distribution; And silicon dioxide makes to form the volumetric expansion that good skeletal support well can cushion silicon between silicon grain and silicon grain, reduces the cubical expansivity of whole silica composite material, effectively reduces the capacity attenuation speed of silica composite material.Argent is conductivity best material in all metals, and argent is enough stable in atmosphere, can not reduce its conductivity because of oxidation.Conducting matrix grain is defined at the argent of the first mixture outer cladding, be convenient to electric transmission, the silicon dioxide that compensate in the composite material of silicon in the first mixture and silicon dioxide does not have the problem of conductivity, make this lithium ion battery negative material have good conductivity, thus improve cycle life and the efficiency for charge-discharge of the lithium ion battery using this material to make.
Embodiment 2
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 1000 orders) is placed in crucible; and put into atmosphere furnace; 1200 DEG C are warmed up under the protection of argon gas atmosphere; heat 0.5 hour at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 10nm, and silicon accounts for 30% of the first mixture quality, and silicon dioxide accounts for 60% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 1000 object particles this second mixture ball milling.
(3) be added to the water by above-mentioned second mixture, then add appropriate nitric acid gold solution, obtain suspension, wherein, in this suspension, the amount of the second mixture is 20g/ml, and the concentration of the gold ion in suspension is 0.001mol/L.Then at 30W/cm
2ultrasonic under the ultrasonic condition of the sound intensity, second mixture is fully disperseed and mixes with nitric acid gold solution, stir and lower drip enough hydrofluoric acid solutions, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 10wt% of 20g according to every gram of gold ion in the described suspension of correspondence.Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with metallic gold at this first mixture.Wherein, the quality of the metallic gold of the first mixture outer cladding accounts for 15% of the quality of lithium ion battery negative material.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1352mAh/g, and the specific discharge capacity after 100 times that circulates is 732mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is that the first mixture obtained after silicon monoxide disproportionated reaction is coated with gold, first mixture mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.The composite material of this silicon and silicon dioxide is generated through high temperature disproportionated reaction by silicon monoxide, and silicon is wherein nano-silicon.In the composite material of silicon and silicon dioxide, silicon accounts for the quality of about 1/3rd, and silicon dioxide accounts for the quality of about 2/3rds.In the composite material of silicon and silicon dioxide, in silica, in doff lithium process, the silicon dioxide in the composite material of silicon and silicon dioxide can stop silicon grain in repeatedly doff lithium process, electrochemistry sintering occur and reunite in silicon distribution; And silicon dioxide makes to form the volumetric expansion that good skeletal support well can cushion silicon between silicon grain and silicon grain, reduces the cubical expansivity of whole silica composite material, effectively reduces the capacity attenuation speed of silica composite material.The conductivity of metallic gold is good, and metallic gold is enough stable in atmosphere, can not reduce its conductivity because of oxidation.Conducting matrix grain is defined in the metallic gold of the first mixture outer cladding, be convenient to electric transmission, the silicon dioxide that compensate in the composite material of silicon in the first mixture and silicon dioxide does not have the problem of conductivity, make this lithium ion battery negative material have good conductivity, thus improve cycle life and the efficiency for charge-discharge of the lithium ion battery using this material to make.
Embodiment 3
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 10000 orders) is placed in crucible; and put into atmosphere furnace; 1100 DEG C are warmed up under the protection of argon gas atmosphere; heat 12 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 1nm, and silicon accounts for 27% of the first mixture quality, and silicon dioxide accounts for 54% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 8000 object particles this second mixture ball milling.
(3) be added to the water by above-mentioned second mixture, then add appropriate platinum chloride solution, obtain suspension, wherein, in this suspension, the amount of the second mixture is 30g/ml, and the concentration of the platinum ion in suspension is 0.005mol/L.Then at 30W/cm
2ultrasonic under the ultrasonic condition of the sound intensity, second mixture is fully disperseed and mixes with platinum chloride solution, stir and lower drip enough hydrofluoric acid solutions, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 8wt% of 40g according to every gram of platinum ion in the described suspension of correspondence.Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with metal platinum at this first mixture.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for 30% of the quality of lithium ion battery negative material.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1415mAh/g, and the specific discharge capacity after 100 times that circulates is 746mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
The structure of the lithium ion battery negative material in the present embodiment is that the first mixture obtained after silicon monoxide disproportionated reaction is coated with platinum, first mixture mainly comprises the composite material of silicon and silicon dioxide, and the composite material of this silicon and silicon dioxide is the basis material of lithium ion battery negative material.The composite material of this silicon and silicon dioxide is generated through high temperature disproportionated reaction by silicon monoxide, and silicon is wherein nano-silicon.In the composite material of silicon and silicon dioxide, silicon accounts for the quality of about 1/3rd, and silicon dioxide accounts for the quality of about 2/3rds.In the composite material of silicon and silicon dioxide, in silica, in doff lithium process, the silicon dioxide in the composite material of silicon and silicon dioxide can stop silicon grain in repeatedly doff lithium process, electrochemistry sintering occur and reunite in silicon distribution; And silicon dioxide makes to form the volumetric expansion that good skeletal support well can cushion silicon between silicon grain and silicon grain, reduces the cubical expansivity of whole silica composite material, effectively reduces the capacity attenuation speed of silica composite material.The conductivity of metal platinum is good, and metal platinum is enough stable in atmosphere, can not reduce its conductivity because of oxidation.Conducting matrix grain is defined in the metal platinum of the first mixture outer cladding, be convenient to electric transmission, the silicon dioxide that compensate in the composite material of silicon in the first mixture and silicon dioxide does not have the problem of conductivity, make this lithium ion battery negative material have good conductivity, thus improve cycle life and the efficiency for charge-discharge of the lithium ion battery using this material to make.
Embodiment 4
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 15000 orders) is placed in crucible; and put into atmosphere furnace; 700 DEG C are warmed up under the protection of argon gas atmosphere; heat 5 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 50nm, and silicon accounts for 25% of the first mixture quality, and silicon dioxide accounts for 50% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 15000 object particles this second mixture ball milling.
(3) above-mentioned second mixture is added to the water, add the mixed solution (in mixed solution, the amount of substance of silver ion and gold ion is than being 1:1) of appropriate silver nitrate and nitric acid gold again, obtain suspension, wherein, in this suspension, the amount of the second mixture is 5g/ml, and the silver ion in suspension and the total concentration of gold ion are 0.008mol/L.Then at 30W/cm
2ultrasonic under the ultrasonic condition of the sound intensity, second mixture is fully disperseed and mixes with the mixed solution of silver nitrate and nitric acid gold, stir the hydrofluoric acid solution that lower dropping is enough, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 12wt% of 30g according to every gram of gold ion or silver ion in the described suspension of correspondence.Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with metal platinum at this first mixture.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for 5% of the quality of lithium ion battery negative material.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1379mAh/g, and the specific discharge capacity after 100 times that circulates is 698mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 5
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 8000 orders) is placed in crucible; and put into atmosphere furnace; 950 DEG C are warmed up under the protection of argon gas atmosphere; heat 6 hours at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 25nm, and silicon accounts for 26% of the first mixture quality, and silicon dioxide accounts for 52% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 10000 object particles this second mixture ball milling.
(3) be added to the water by above-mentioned second mixture, then add appropriate liquor argenti nitratis ophthalmicus, obtain suspension, wherein, in this suspension, the amount of the second mixture is 5g/ml, and the concentration of the silver ion in suspension is 0.001mol/L.Then at 30W/cm
2ultrasonic under the ultrasonic condition of the sound intensity, the second mixture is made fully to disperse and mix with liquor argenti nitratis ophthalmicus, stir and lower drip enough hydrofluoric acid solutions, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 13wt% of 10g according to every gram of silver ion in the described suspension of correspondence.Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with argent at this first mixture.Wherein, the quality of the argent of the first mixture outer cladding accounts for 20% of the quality of lithium ion battery negative material.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1423mAh/g, and the specific discharge capacity after 100 times that circulates is 872mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 6
The present embodiment provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
(1) silicon monoxide powder (particle diameter is 12000 orders) is placed in crucible; and put into atmosphere furnace; 1000 DEG C are warmed up under the protection of argon gas atmosphere; heat 1 hour at such a temperature; silicon monoxide generation disproportionated reaction generates the composite material of silicon and silicon dioxide; because silicon monoxide can be reunited after high temperature sintering, so the particle diameter of the second mixture finally obtained is comparatively large, this second mixture comprises the composite material of the unreacted silicon monoxide of part and silicon and silicon dioxide.Find after testing: in the composite material of silicon and silicon dioxide, silicon is distributed in silica substrate, and the particle diameter of described silicon is nanoscale 6nm, and silicon accounts for 31% of the first mixture quality, and silicon dioxide accounts for 62% of the first mixture quality.
(2) the second mixture is added in ball grinder, then add 4 times of ball milling pearls to the weight of the second mixture (large and small ball milling pearl adds according to 1:1 ratio).Ball grinder is placed on planetary ball mill, by the second mixture ball milling 12 hours under the rotating speed of 300 revs/min, becomes particle diameter to be 12000 object particles this second mixture ball milling.
(3) be added to the water by above-mentioned second mixture, then add appropriate platinum chloride solution, obtain suspension, wherein, in this suspension, the amount of the second mixture is 15g/ml, and the concentration of the platinum ion in suspension is 0.002mol/L.Then at 30W/cm
2ultrasonic under the ultrasonic condition of the sound intensity, second mixture is fully disperseed and mixes with platinum chloride solution, stir and lower drip enough hydrofluoric acid solutions, and the addition of hydrofluoric acid adds the hydrofluoric acid of the 15wt% of 40g according to every gram of platinum ion in the described suspension of correspondence.Second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material being coated with metal platinum at this first mixture.Wherein, the quality of the metal platinum of the first mixture outer cladding accounts for 10% of the quality of lithium ion battery negative material.
According to the method preparing button cell in embodiment 1, the obtained lithium ion battery negative material of the present embodiment is used to make button cell, and charge-discharge performance test is carried out to this battery: first discharge specific capacity reaches 1579mAh/g, and the specific discharge capacity after 100 times that circulates is 1015mAh/g.
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises above-mentioned lithium ion battery negative material.
Embodiment 7
The present embodiment provides a kind of lithium ion battery, its negative pole contains lithium ion battery negative material described in the above embodiments 1 ~ 6 and graphite, wherein, the quality of lithium ion battery negative material accounts for 20% of the mixture gross mass of lithium ion battery negative material and graphite.
Lithium ion battery in the present embodiment, in doff lithium process, silicon dioxide in negative pole can stop silicon grain electrochemistry sintering occurs in repeatedly doff lithium process and reunites, and silicon dioxide makes to form the volumetric expansion that good skeletal support well can cushion silicon grain between silicon grain and silicon grain, and then effectively alleviate the capacity attenuation of whole negative material of lithium ion battery; Graphite in negative pole does not almost have bulk effect.
Embodiment 1 ~ 6 prepare lithium ion battery negative material first efficiency lower than 80%, and existing commercialization graphite cathode material first efficiency be greater than 85%, high-end graphite cathode material first efficiency is greater than 95%.High-end graphite cathode material in the lithium ion battery negative material prepare above-described embodiment 1 ~ embodiment 6 and the present embodiment is jointly as the negative material of lithium ion battery, the efficiency first of this mixing negative material is greater than 92%, embedding lithium specific capacity is 540mAh/g first, and the specific discharge capacity after 100 times that circulates is 485mAh/g.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. a lithium ion battery negative material, is characterized in that, its structure is one or more that the first mixture obtained after silicon monoxide disproportionated reaction is coated with in silver, gold, platinum.
2. lithium ion battery negative material according to claim 1, is characterized in that, the particle diameter of described silicon monoxide is 1000 ~ 15000 orders.
3. lithium ion battery negative material according to claim 1, is characterized in that, the gross mass of one or more of the silver of described first mixture outer cladding, gold, platinum accounts for 0.5 ~ 30% of described lithium ion battery negative material quality.
4. a preparation method for the lithium ion battery negative material described in claims 1 to 3 any one, is characterized in that, comprises the following steps:
(1) the second mixture is obtained after silicon monoxide generation disproportionated reaction;
(2) one or more in silver salt, golden salt, platinum salt and described second mixture are added to the water obtain suspension, add hydrofluoric acid again, described second mixture part is corroded and obtains the first mixture, and obtains the lithium ion battery negative material of one or more that is coated with at this first mixture in silver, gold, platinum.
5. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, also comprises step (i) between described step (1) and described step (2): described second mixture being worn into particle diameter is 1000 ~ 15000 object particles.
6. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, described in described step (1), the temperature of silicon monoxide disproportionated reaction is 700 ~ 1200 DEG C, and the time is 0.5 ~ 24 hour.
7. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, the addition of hydrofluoric acid described in described step (2) adds the hydrofluoric acid of the 5 ~ 15wt% of 10 ~ 40g according to every gram of metal ion in the described suspension of correspondence.
8. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, the total concentration of one or more in the silver ion in suspension described in described step (2), gold ion, platinum ion is 0.0001 ~ 0.01mol/L.
9. the preparation method of lithium ion battery negative material according to claim 4, is characterized in that, described in described step (2), described in suspension, the amount of the second mixture is 5 ~ 30g/ml.
10. a lithium ion battery, is characterized in that, its negative pole comprises the lithium ion battery negative material described in claims 1 to 3 any one.
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