CN102569768A - High-specific-area carbon/metallic oxide composite electrode material of lithium battery, electrode and preparation methods for high-specific-area carbon/metallic oxide composite electrode material and electrode - Google Patents
High-specific-area carbon/metallic oxide composite electrode material of lithium battery, electrode and preparation methods for high-specific-area carbon/metallic oxide composite electrode material and electrode Download PDFInfo
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- CN102569768A CN102569768A CN2012100209639A CN201210020963A CN102569768A CN 102569768 A CN102569768 A CN 102569768A CN 2012100209639 A CN2012100209639 A CN 2012100209639A CN 201210020963 A CN201210020963 A CN 201210020963A CN 102569768 A CN102569768 A CN 102569768A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 62
- 229910002090 carbon oxide Inorganic materials 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 51
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 13
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 12
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000004408 titanium dioxide Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- HTCXJNNIWILFQQ-UHFFFAOYSA-M emmi Chemical compound ClC1=C(Cl)C2(Cl)C3C(=O)N([Hg]CC)C(=O)C3C1(Cl)C2(Cl)Cl HTCXJNNIWILFQQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- XTYRIICDYQTTTC-UHFFFAOYSA-N 1-(dimethylamino)-2-methylpropan-2-ol Chemical compound CN(C)CC(C)(C)O XTYRIICDYQTTTC-UHFFFAOYSA-N 0.000 description 1
- 235000009300 Ehretia acuminata Nutrition 0.000 description 1
- 244000046038 Ehretia acuminata Species 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013391 LizN Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MWOHGFBLWUZMBB-UHFFFAOYSA-N [Cu+].C(CCC)P(CCCC)CCCC.C(CCC)P(CCCC)CCCC Chemical compound [Cu+].C(CCC)P(CCCC)CCCC.C(CCC)P(CCCC)CCCC MWOHGFBLWUZMBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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 high-specific-area carbon/metallic oxide composite electrode material of a lithium battery, an electrode and preparation methods for the high-specific-area carbon/metallic oxide composite electrode material and the electrode. A metallic oxide is deposited on high-specific-area carbon powder by using an atomic layer deposition method, and the mass ratio of a metallic oxide film to high-specific-area carbon is between 70 percent and 90 percent. The invention also provides a method for preparing the high-specific-area carbon/metallic oxide composite electrode material by using the atomic layer deposition method, and a method for preparing the electrode by using the high-specific-area carbon/metallic oxide composite electrode material. The high-specific-area carbon/metallic oxide composite electrode material has a high-mass-ratio characteristic, and the lithium battery prepared from the high-specific-area carbon/metallic oxide composite electrode material has a long cycle life and high capacitance stability.
Description
Technical field
The present invention relates to high specific area carbon/metal oxide composite electrode material, electrode of lithium ion battery and preparation method thereof.
Background technology
Lithium battery is the core component of present electric automobile, as the ripe relatively green energy resource of technology, receives increasing concern.By the hybrid system that super capacitor and lithium battery are formed, can combine both advantages and realize the storage of high-power high-energy.For example, in electric automobile, super capacitor can quicken and the climbing process in energy is provided, and the energy storage that motor reverses will brake the time; Lithium battery then provides energy for the long distance travel that automobile continues.But lithium battery still faces problems at present, and one of them maximum problem is the capacity and the stability of electrode.In traditional Anode of lithium cell, use graphite as material usually, its theoretical value capacity is merely 380mAh/g, can not well satisfy growing capacity requirement at present.
Except that carbon back or graphite-based anode material; Application for potential anode; Carried out the research of other materials; The inorganic material that for example comprises metal oxide, metal nitride, metal sulfide etc., and a series of metals, metal alloy and the intermetallic compound of receivability lithium atom/ion.Especially, will have composition formula Li
aThe lithium alloy of A (A is for example Al of metal, and " a " satisfies 0＜a＜5) is studied as potential anode material.This type anode material has higher theoretical capacity, for example Li
4Si (3,829mAh/g), Li
4.4Si (4,200mAh/g), Li
4.4Ge (1,623mAh/g), Li
4.4Sn (993mAh/g), Li
3Cd (715mAh/g), Li
3Sb (660mAh/g), Li
4.4Pb (569mAh/g), LiZn (410mAh/g) and Li
3Bi (385mAh/g).Yet, for the anode that constitutes by these materials, because the expansion and the contraction of anode between adsorption cycle are conciliate in lithium ion absorption, along with pulverize (fragmentation of alloying pellet) of charging and discharge cycles.Said expansion and shrink is also tended to cause the contact minimizing between contacting of particle and particle or anode and its collector or to lose.These detrimental effects cause the significantly charge-discharge cycles life-span of shortening.
For overcoming the problem relevant, proposed and to be used as anode material by the compound that load has the little electro-chemical activity particle of less activity or nonactive matrix to constitute with so mechanical deterioration.The example of these active particles is Si, Sn, SnO
2, TiO
2, SiO
2, MnO
2, CuO, Co
3O
4, NiO, Fe
2O
3, Fe
3O
4, ZnO, MoO
3, RuO
2Or WO
3Yet; The combination electrode of most prior art has defective in some aspects; For example; In most of situations, be lower than gratifying reversible capacity, the cyclical stability of difference, high irreversible capacity, during lithium ion inserts and deviates from step, reduce ineffectivity and/or undesirable side effect of internal stress or strain.
For example, at United States Patent(USP) No. 6,007, disclosed in 945 (on December 28th, 1999) like people such as Jacobs, the solid solution that in the negative electrode of lithium rechargeable battery, uses titanium dioxide and tin ash is as anode active material.Density by the negative electrode of above-mentioned manufacturing is 3.65g/cm
3, and discovery contains the TiO of 39: 61 weight ratios
2-SnO
2The reversible capacity of negative electrode be 1130mAh/cm
3This equates 309.6mAh/g, although calculate the energy density that the lithium rechargeable battery that is obtained has 207 watts-hour/liters.In addition, the reaction of the nano particle of anode material and electrolyte causes the long-term effectiveness that reduces during charge-discharge cycles.
,,, then evaporate, heat and further handle described in 448 (on November 7th, 2000) at United States Patent(USP) No. 6,143 like people such as Fauteux, form compound through in water, carbon being mixed with slaine.This process has produced has the compound in high-specific surface area crack perhaps, and said hole is always not preferred.Having reported best got capacity is 750-2,000mAh/cm
3For 4g/cm
3Density, this is hinting that heap(ed) capacity is 500mAh/g.
At United States Patent(USP) No. 6,103, in 393 (on Augusts 15th, 2000), people such as Kodas make this mixture become aerosol and heat then the carbon-metal particle are provided through reactant is mixed.Each particle contain carbon mutually with metal mutually.This research relates generally to platinum, silver, palladium, ruthenium, osmium and their alloy of the carbon load that is used for electro-catalysis purpose (for example being used for fuel cells applications).
At United States Patent(USP) No. 7,094, in 499 (on Augusts 22nd, 2006), Hung discloses the method that forms composite anode materials.This step comprises selects the component part of material with carbon element as compound; The selected material with carbon element of chemical treatment is to receive nano particle; The outer surface of the material with carbon element of the nano particle that nano particle is included in chemically treated material with carbon element and the nano surface particle is included in from having is removed.The material and the lithium alloyage that will constitute by nano particle.Gained carbon/nano particle composite anode does not show any obvious raising of capacity, is lower than 400mAh/g mostly.
In a word, do not prove in the prior art that composite material has required all of the anode that is used for lithium ion battery or most performance.Therefore, there are needs to lithium ion cell electrode with high cycle life, high power capacity stability.Also exist being easy to or preparing easily the needs of the method for this material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high specific area carbon/metal oxide composite electrode material; And the electrode that adopts high specific area carbon/metal oxide composite electrode material manufacture, overcome the low cycle life of existing lithium ion cell electrode, the defective of low capacity stability.
For solving the problems of the technologies described above; The present invention proposes a kind of high specific area carbon/metal oxide composite electrode material; It is characterized in that, comprising: the high-specific surface area carbon dust is deposited on the metal-oxide film on the high-specific surface area carbon dust with atomic layer deposition method; The thickness of said metal-oxide film is 1-10nm, and said metal oxide is thin/and the mass ratio of high specific area carbon is 70%--90%.
Preferably, between said high-specific surface area carbon dust and metal-oxide film, there is the alundum (Al adhesive layer, the about 0.1-0.5nm of the thickness of said alundum (Al adhesive layer.
Said metal oxide comprises TiO
2, SnO
2, SiO
2, MnO
2, CuO, Co
3O
4, NiO, Fe
2O
3, Fe
3O
4, ZnO, MoO
3, RuO
2Or WO
3, select to know wherein a kind of.
Said high-specific surface area (m
2/ g) carbon dust material is preferably Graphene, CNT, mesoporous carbon; Activated carbon, carbon nanocoils, carbon black; Acetylene black or graphite utilize their high-specific surface area, a large amount of open channel, stable chemical properties and favorable mechanical and electric conductivities, with them as template; Utilize wherein middle micropore and large micropore structure, allow nano material and electrolyte to get into and provide the conduction approach.
The present invention provides said high specific area carbon/metal oxide composite electrode preparation methods simultaneously, may further comprise the steps:
A, on the high-specific surface area carbon dust, deposit the alundum (Al adhesive layer that thickness is 0.1-.5nm with atomic layer deposition method;
B, on the high-specific surface area carbon dust of the said alundum (Al adhesive layer of spreading, to deposit thickness with atomic layer deposition method be the metal-oxide film of 1-10nm.
Promptly obtain said high specific area carbon/metal oxide composite electrode material.
The present invention also provides a kind of method of the preparation electrode of lithium cell that utilizes said high specific area carbon/metal oxide composite electrode material simultaneously, may further comprise the steps:
High specific area carbon/metal oxide complex composition and CNT are proportionally mixed; Wherein the mass range of CNT is between 3% to 10%; Then and lauryl sodium sulfate (sodium dodecyl sulfate) mix; And making its dispersing and mixing even with supersonic oscillations, said lauryl sodium sulfate is from 1% to 100% with respect to the mass ratio of high specific area carbon/metal oxide complex composition.After this, obtain electrode with vacuum filtration.
Preferably, the quality accounting of above-mentioned CNT is preferably 5%.
Preferably, said lauryl sodium sulfate is 1% with respect to the mass ratio of high specific area carbon/metal oxide complex composition.
The present invention also provides the another kind of method of the preparation electrode of lithium cell that utilizes said high specific area carbon/metal oxide composite electrode material simultaneously, may further comprise the steps:
With high specific area carbon/metal oxide complex composition; The carbon black conductive agent also has polyvinylidene fluoride (polyvinylidenefluoride; Hereinafter referred PVDF) adhesive is according to 80: 10: 10 mixed, and makees solvent with N-methyl pyrrolidone (N-methyl-2-pyrrolidone); After evenly mixing slurry is applied on the Copper Foil, and in vacuum chamber, is heated to 120 degree more than 12 hours; Roll contacting with 20Mpa pressure afterwards with intensifier electrode and current-collector.
The present invention through use atomic layer deposition method with metal oxide nanoparticles or thin film deposition to the open architecture of high-specific surface area material with carbon element; And the thickness that can realize controlling nano particle or film is to the Ethylmercurichlorendimide rank; Increase the structural stability of metal oxide on high specific area carbon; And improved cycle efficieny, and and can make full use of the high-specific surface area structure, make compound density (g/cm
3) can reach maximum optimum.The present invention uses ALD alundum (Al adhesive layer, only reacts on the defective surface of Graphene to prevent titanium dioxide.Through experimental verification, the introducing of alundum (Al has not only improved the uniformity of metal oxide nanoparticles or film, and has improved the capacity invertibity and the stability of high-specific surface area carbon electrode material.
Embodiment
The high specific area carbon of this embodiment is example with the Graphene, and metal oxide is that example specifies with titanium dioxide.The shape of lithium battery can be cylindrical, square, button-type etc.The invention is not restricted to any cell shapes or structure.
The present invention is deposited on titanium deoxid film or titania nanoparticles on the graphene powder with rotary or fluidized bed type ALD reacting furnace.But, because Graphene bottom plane is not easy to react very much, therefore, passing through the titanium dioxide that the ALD deposition forms and will be difficult to form initial nucleus at Graphene.Among the present invention, use ALD alundum (Al adhesive layer, only react on the defective surface of Graphene to prevent titanium dioxide.Through experimental verification, the introducing of alundum (Al has not only improved TiO
2The uniformity, and improved capacity invertibity and the stability of Graphene itself as electrode material.
Al
2O
3The preparation process of adhesive layer is:
1. put into graphene powder at the ALD reacting furnace, inject the TMA reacting gas then, reach 1Torr, close all reacting furnace valves then, leave standstill 90-180 second, preferred 120 seconds up to air pressure to reaction vessel;
2. be evacuated down to 0.1Torr and discharge unnecessary TMA, leave standstill 90-180 second, preferred 120 seconds;
3. inject steam up to 1Torr.Close the valve of all reacting furnaces then, left standstill 120 seconds;
4. vacuumize the discharge superfluous water and reach 0.1Torr, leave standstill 90-180 second, preferred 120 seconds up to air pressure.
Four steps of above 1-4 are called an ALD circulation.Typical A l
2O
3Growth rate is the every circulations of 1.1 to 1.2 Ethylmercurichlorendimides.Cycle-index can determine as required, make Al
2O
3Thickness is about 0.1-0.5nm.ALD is grown in the 120-180 ℃ of scope.Reacting furnace is rotary or fluidized bed type.
Then, on the graphene powder that applies the alundum (Al adhesive layer, (ALD) carries out electroless copper deposition operation to titanium dioxide with atomic layer deposition method.TiCl
4With water as reactant.Typical TiOA
2Growth rate is the every circulation of 0.6 Ethylmercurichlorendimide.
Preparation process is a: put into the graphene powder that applies the alundum (Al adhesive layer at the ALD reacting furnace, inject TiCl then
4Reacting gas reaches 1Torr to reaction vessel up to air pressure, closes all reacting furnace valves then, leaves standstill 90-180 second, preferred 120 seconds; B. be evacuated down to 0.1Torr to discharge unnecessary TiCl
4, leave standstill 90-180 second, preferred 120 seconds; C. inject steam up to 1Torr.Close the valve of all reacting furnaces then, leave standstill 90-180 second, preferred 120 seconds; D. vacuumize the discharge superfluous water and reach 0.1Torr, leave standstill 90-180 second, preferred 120 seconds up to air pressure.Above four steps of a-d are called an ALD circulation.Cycle-index can be according to the thickness decision of titanium dioxide.The thickness of preferred titanium dioxide is 1-10nm, and optimum is 5nm.The ALD Growth Control is in 120-180 ℃ of scope, and reacting furnace is rotary or fluidized bed type.Desirable titanium dioxide ALD growth sedimentation mechanism is as follows:
n(-OH)(s)+TiCl
4(g)→(-O-)
nTiCl
4-n(s)+nHCl(g) (1)
(-O-)
nTiCl
4-n(s)+(4-n)H
2O(g)→(-O-)
nTi(OH)
4-n(s)+(4-n)HCl(g) (2)
N=1-3 wherein.
Above method except that being applicable to titanium dioxide and the Graphene, can also Graphene being replaced with other high-specific surface area material with carbon element, replaces with other metal oxide and the different valence link oxides of respective metal element thereof with titanium dioxide, like SnO
2, SiO
2, MnO
2, CuO, Co
3O
4, NiO, Fe
2O
3, Fe
3O
4, ZnO, MoO
3, RuO
2Or WO
3For example,
SnO
2Available SnCl
4And H
2O
2Obtain 350 ℃ of reactions.SiO
2Can use SiCl
4And H
2O obtains 400 ℃ of reactions.CuO can use bis (tri-n-butylphosphane) copper (I) acetylacetonate and O
2Obtain 160 ℃ of reactions.MnO
2Can use Mn (thd)
3(Hthd=2,2,6,6-tetramethylheptan-3,5-dione) and O
3Obtain 150 ℃ of reactions.Co
3O
4Available Co (thd)
2(Hthd=2,2,6,6-tetramethylheptan-3,5-dione) and O
3Obtain 150 ℃ of reactions.NiO can use Ni (dmamp)
2(dmamp, 1-dimethylamino-2-methyl-2-propanolate) and H
2O obtains 120 ℃ of reactions.Fe
2O
3And Fe
3O
4Available ferrocene (Fe (C
5H
5)
2) and O
3Obtain respectively 150 ℃ of reactions.ZnO can use diethylzinc and H
2O obtains 120 ℃ of reactions.MoO
3Available molybdenum hexacarbonyl (Mo (CO)
6) and O
3, H
2The mixture of O obtains 163 ℃ of reactions.RuO
2Available bisethyl-cyclopentadienyl ruthenium (Ru [(C
2H
5) C
5H
4)]
2) and H
2O obtains 280 ℃ of reactions.WO
3Available WF
6And H
2O obtains 200 ℃ of reactions.Its concrete course of reaction and TiO
2Identical, so do not give unnecessary details.
The preparation of graphene powder
Graphene powder among the present invention utilizes hot soarfing to leave technology or chemical reduction method preparation, and all the other high-specific surface area carbon structures can be bought from the market.
The preparation of electrode of lithium cell
Electrode of lithium cell has two kinds of preparation methods:
Method (1), be mixed with the preparation of the electrode of exempting from adhesive (CNTs-assist binder-free electrodes) of CNT
High specific area carbon/metal oxide complex composition and CNT are proportionally mixed; Wherein the mass range of CNT is between 3% to 10%; Be preferably 5%; Then and lauryl sodium sulfate (sodium dodecyl sulfate) mix, and make its dispersing and mixing even with supersonic oscillations, lauryl sodium sulfate is from 1% to 100% with respect to the mass ratio of high specific area carbon/metal oxide complex composition.After this, obtain electrode with vacuum filtration.Electrode is used deionized water wash, again dry heat in ar gas environment.In glove box, be assembled into button cell at last.The method also has current-collector without conductive agent and adhesive, therefore can improve energy density greatly, reduces the material cost.
Method (2), with high specific area carbon/metal oxide complex composition; The carbon black conductive agent also has polyvinylidene fluoride (polyvinylidene fluoride; Hereinafter referred PVDF) adhesive is according to 80: 10: 10 mixed, and makees solvent with N-methyl pyrrolidone (N-methyl-2-pyrrolidone).After evenly mixing slurry is applied on the Copper Foil, and in vacuum chamber, is heated to 120 degree more than 12 hours.Roll contacting with 20Mpa pressure afterwards with intensifier electrode and current-collector.In glove box, be assembled into button cell at last.
Below be based on the test result of the parameter comparing embodiment between the data of the electrode that nano-metal-oxide/grapheme material that solution reaction obtains and this method obtain.
In the TiO2/ Graphene that obtains with the ALD method, the mass ratio of TiO2 can only obtain 50% and solwution method is the highest usually up to 80% even higher, and additive method is then lower.Therefore, ALD method gained capacity can be near the metal oxide theoretical value, and its compound capacity of additive method reaches half its metal oxide theoretical value at most.SnO with this method preparation
2The capacity of/Graphene reaches 800mAh/g, be the twice of existing graphite electrode, and the same compound thing that common additive method obtains is no more than 500mAhg at most
-1Under the high current charge-discharge situation, even after the 150 circle circulations, capacity does not fail basically.And the capacity based on solwution method of existing report, under little electric current charge status, its cycle characteristics only limits to about 50 circles.The TiO2/ Graphene capacity of anatase form discharges and recharges at 30C still has 100mAh/g nearly under the condition, and carbon is merely 20mAh/g under the same terms.
In addition, the method for ALD can the required crystal type of selective growth, from amorphous state to each quasi-crystalline.Additive method then is difficult to control.Solwution method tends to form each quasi-crystalline.
For the electrode of other kinds metal oxide/graphene complex preparation, equally also have high power capacity, stable strong advantage.Concrete each characteristic index is as shown in the table:
Described embodiment should think exemplary, and whether applicant's claim should or not be limited to the details of said exemplary embodiment scheme.Can multiple change and distortion be contained in the said embodiment, comprise in the different exemplary the characteristic described separately make up.Therefore, scope of the present invention is intended to go book to limit right subsequently.In addition, can consider with separately or the concrete characteristic of describing as embodiment middle part branch with other separately the characteristic of description or the part in other embodiment make up, even not mentioned this concrete characteristic of further feature and embodiment.
Claims (10)
1. high specific area carbon/metal oxide composite electrode material; It is characterized in that; Comprise: the high-specific surface area carbon dust; Be deposited on the metal-oxide film on the high-specific surface area carbon dust with atomic layer deposition method, the thickness of said metal-oxide film is 1-10nm, and said metal oxide is thin/and the mass ratio of high specific area carbon is 70%--90%.
2. high specific area carbon as claimed in claim 1/metal oxide composite electrode material; It is characterized in that; Between said high-specific surface area carbon dust and metal-oxide film, there is the alundum (Al adhesive layer, the about 0.1-0.5nm of the thickness of said alundum (Al adhesive layer.
3. according to claim 1 or claim 2 high specific area carbon/metal oxide composite electrode material is characterized in that said metal oxide is selected from TiO
2, SnO
2, SiO
2, MnO
2, CuO, Co
3O
4, NiO, Fe
2O
3, Fe
3O
4, ZnO, MoO
3, RuO
2Or WO
3
4. according to claim 1 or claim 2 high specific area carbon/metal oxide composite electrode material is characterized in that the carbon dust material of said high-specific surface area; Be preferably Graphene, CNT, mesoporous carbon, activated carbon; Carbon nanocoils, carbon black, acetylene black or graphite.
5. high specific area carbon as claimed in claim 3/metal oxide composite electrode material is characterized in that, the carbon dust material of said high-specific surface area is preferably Graphene, CNT, mesoporous carbon, activated carbon, carbon nanocoils, carbon black, acetylene black or graphite.
6. said high specific area carbon/metal oxide composite electrode preparation methods is characterized in that, may further comprise the steps: a, on the high-specific surface area carbon dust, deposit the alundum (Al adhesive layer that thickness is 0.1-.5nm with atomic layer deposition method; B, on the high-specific surface area carbon dust of the said alundum (Al adhesive layer of spreading, to deposit thickness with atomic layer deposition method be the metal-oxide film of 1-10nm.
7. method of utilizing said high specific area carbon/metal oxide composite electrode material preparation electrode of lithium cell; It is characterized in that; May further comprise the steps: high specific area carbon/metal oxide complex composition and CNT are proportionally mixed; Wherein the mass range of CNT is between 3% to 10%; Then and lauryl sodium sulfate (sodium dodecyl sulfate) mix, and make its dispersing and mixing even with supersonic oscillations, said lauryl sodium sulfate is from 1% to 100% with respect to the mass ratio of high specific area carbon/metal oxide complex composition; Then, obtain electrode with vacuum filtration.
8. the method for high specific area carbon as claimed in claim 7/metal oxide composite electrode material preparation electrode of lithium cell is characterized in that the quality accounting of said CNT is preferably 5%.
9. the method for high specific area carbon as claimed in claim 9/metal oxide composite electrode material preparation electrode of lithium cell; It is characterized in that said lauryl sodium sulfate is 1% with respect to the mass ratio of high specific area carbon/metal oxide complex composition.
10. method of utilizing said high specific area carbon/metal oxide composite electrode material preparation electrode of lithium cell; It is characterized in that; May further comprise the steps: with high specific area carbon/metal oxide complex composition; The carbon black conductive agent also has the mixed of polyvinylidene fluoride adhesive according to 80:10:10, and makees solvent with the N-methyl pyrrolidone; After evenly mixing slurry is applied on the Copper Foil, and in vacuum chamber, was heated to 120 degree at least 12 hours; Roll contacting with 20Mpa pressure afterwards with intensifier electrode and current-collector.
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