CN108364806A - A kind of tree-shaped three-dimensional structure metal material and preparation method thereof and application in the battery - Google Patents
A kind of tree-shaped three-dimensional structure metal material and preparation method thereof and application in the battery Download PDFInfo
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- CN108364806A CN108364806A CN201810131153.8A CN201810131153A CN108364806A CN 108364806 A CN108364806 A CN 108364806A CN 201810131153 A CN201810131153 A CN 201810131153A CN 108364806 A CN108364806 A CN 108364806A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007769 metal material Substances 0.000 title claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003990 capacitor Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 238000005234 chemical deposition Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000002659 electrodeposit Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims 1
- 238000012512 characterization method Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 14
- 238000004146 energy storage Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- -1 nickel foam Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012360 testing method 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of tree-shaped three-dimensional structure metal materials and preparation method thereof and application in the battery.Include the following steps:(1)Using metallic conductor as substrate, by the method for chemical deposition, tree-shaped three-dimensional structure metal material is grown on metallic conductor surface;(2)By electrode active material by assembling or being grown directly upon the inside of tree-shaped three-dimensional structure metal material, after drying process tabletting obtain electrode.The method that the present invention prepares battery or electrode for capacitors using tree-shaped three-dimensional structure metal material as battery current collector, this method can realize the direct-assembling of electrode active material, can also realize that electrode active material reacts in situ and prepare electrode.By the application of electrode to it is secondary can be in charge and discharge battery or capacitor, it will be apparent that improve the comprehensive performance of battery.
Description
Technical field
The invention belongs to energy storage fields, specifically, being related to a kind of metal collection with tree-shaped three-dimensional structure material
The method that stream device prepares battery or electrode for capacitors.
Background technology
It is secondary can charge and discharge battery(Lithium-sulfur cell, lithium sode cell and sodium-ion battery etc.)And capacitor(Electrochemistry and super
Capacitor)The energy storage equipment of the advantages that Deng these high-energy densities, long circulation life, quick charge, memory effect unobvious exists
Mobile electronic device, means of transport, mobility energy storage system, medical instrument, the purposes of field work are more and more extensive.At this
In the energy storage equipment of a little recyclable charge and discharge, current collector is an important component, and there are energy storage equipments just(It is cloudy), it is negative
(Sun)The two poles of the earth.Usual current collector selects the material of high conductivity, such as copper, aluminium, nickel or stainless steel etc..However, with portable
The fast development of electronic equipment and New-energy electric vehicle, market is to the long-life of energy storage equipment and high stability and large capacity
Demand show especially urgent, to which the person that excites Technological research is to the research enthusiasm of various building blocks in energy storage equipment,
Make it have better comprehensive electrochemical.And the hot spot of current research focuses on anode and cathode active materials etc..Previous grinds
Study carefully as a result, it has been found that the stability of positive and negative electrode electrode directly affects the comprehensive life of energy storage means in fact.Current energy storage means electrode
Preparation be typically on current collector electrode coated material, since it is desired that electrode material to be fixed on to smooth current collector(Such as copper
Foil, aluminium foil etc.)On, therefore polymer binder(Kynoar(PVDF)Or cellulose)It is essential.Such electrode dress
The battery matched is in the charge and discharge process of cycle, the charge and discharge process especially under high current density, with electrode active material
Volume change and the long-time infiltration of electrolyte cause coat to be more easily damaged or structural breakdown, to fall off.It makes
It at energy irreversible loss, and causes battery capacity loss, chemical property unstable, or even short circuit occurs to cause safety
The problems such as problem.
Existing researcher has selected foam copper(S. L. Jing, Journal of Materials Chemistry
A, 2014, 2, 16360-16364.)Or the foam metals such as nickel foam, as current collector, result of study shows foam metal
The performance of battery can be effectively promoted as battery current collector, but because of the structure that foam metal has macropore penetrating, to
And do not have universal usability.Foam metal also has the relevant patent to be reported as the current collector of battery(Such as Zhao Chunsong
Deng using business three-dimensional foam metal material as current collector, directly by active material assembling, then tabletting becomes lithium ion battery
Electrode《CN104577136A, battery current collector with three-dimensional structure and its preparation method》.Also some other material of someone
Expect the current collector as battery, graphene(T. Xu,Chinese Journal of Chemistry, 2017, 35, 1575-
1585.), carbon cloth, carbon fiber(Y. Z. Wan, Journal of Materials Chemistry A, 2015, 3,
15386-15393.)Or carbon nanotube(M. Y. Li, Acs Nano, 2017, 11, 4877-4884.)Deng the type
Preparing for material is more complicated, while being difficult to realize active material and accurately controlling.
Exploitation new material is used for energy storage equipment as current collector, for improving performance and the guarantee of energy storage equipment as a result,
Its safety has great importance.Early stage has the strange D Luo Pating of plucked instrument and applies《CN201080014859.8 for battery and
Porous three-dimensional copper, tin, copper and tin, copper and tin cobalt and the copper and tin cobalt Ti electrode of ultra-capacitor》Patent of invention, but the patent is
Elaborate that three-dimensional porous material can be used as the electrode of battery and ultra-capacitor.Meanwhile this research team finds porous three-dimensional copper material
Material has good performance in terms of heat transfer(Lv Shushen etc., CN201610828 565.8;One kind has natural multi-resolution tree dendritic
Micropin wing copper surface texture and preparation method thereof;Mo Dongchuan etc., CN201610829432.2, a kind of double scales of the micro-nano of single layer are strong
Change boiling heat transfer copper surface texture and preparation method thereof).But above-mentioned these be only disclose three-dimensional material with accumulation of energy and
Performance in terms of heat transfer, there is no further application studies.
Invention content
The purpose of the present invention is overcoming the shortcomings of in existing 3-d tree-like material application technical research, provide a kind of using tree
Shape three-dimensional structure metal material is come the method for preparing electrode, to obtain high-energy density, long circulation life, quick charge etc. more
High-performance and safer secondary cell or capacitor.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of preparation method of tree-shaped three-dimensional structure metal material electrode, includes the following steps:(1)Using metallic conductor as substrate,
By the method for chemical deposition, tree-shaped three-dimensional structure metal material is grown on metallic conductor surface;(2)Electrode active material is led to
Cross the inside for assembling or being grown directly upon tree-shaped three-dimensional structure metal material, after drying process tabletting obtain electrode.This is tree-shaped
Electrode active material can be fixed therein portion by three-dimensional structure metal material, due to the structure of the tree-shaped three-dimensional of itself, can be carried
For the inside specific surface of bigger, promotes the distribution of electrode active material inside tree-shaped three-dimensional structure metal material evenly, carry
Electric conductivity between high electrode active material and tree-shaped three-dimensional structure metal material, and promote the quick biography of lithium ion inside it
It passs, meanwhile, this three-dimensional structure can more effectively inhibit the dusting of electrode active material and fall off.
In above-mentioned preparation method, step(1)The metallic conductor is copper foil, aluminium foil, nickel foil, foam copper, foamed aluminium
Or nickel foam.
In above-mentioned preparation method, step(1)After the chemical deposition, metal material is taken out, is washed with deionized water
Remained on surface electrodeposit liquid, drying;Then it is heat-treated in a reducing atmosphere, reducing atmosphere is 2% ~ 10% volumetric concentration
H2/N2The H of gaseous mixture or 2% ~ 15% volumetric concentration2The temperature of/Ar gaseous mixtures, heat treatment is 500-850 DEG C.
In above-mentioned preparation method, step(2)The electrode active material includes positive electrode, negative material or capacitance
Device electrode material;The positive electrode is LiMn2O4, cobalt acid lithium, lithium nickelate, cobalt nickel ion doped(Ternary material)Or LiFePO4;
The negative material is carbon material(Graphite-like, hard carbon, porous carbon, agraphitic carbon, carbon nanotube, graphene etc.), metal oxidation
Object, metal carbonate, metal sulfide, metal nitride, Alloy Heterojunction structure compound or silicon systems material(It is compound including silicon-carbon
Material, nano-silicon, silicon carbide, silica etc.);The capacitor electrode material is absorbent charcoal material, carbon aerogel electrodes material
Material, carbon nanotube, activated carbon fibre, graphene, metal oxide materials or conducting polymer materials.
In above-mentioned preparation method, step(2)The electrode active material is completed after preparing and characterizing, and solvent is distributed to
Middle realization assembling, electrode is obtained by tabletting;The solvent is water, ethyl alcohol, ether, acetone or N-methyl pyrrolidones.
In above-mentioned preparation method, step(2)It is disperse in tree-shaped three-dimensional structure after the electrode active material synthesis
In metal material, then drying, compressing tablet process obtain electrode.
In above-mentioned preparation method, step(2)The reactant of the electrode active material is in tree-shaped three-dimensional structure metal
It is directly reacted in material, in situ to obtain electrode active material, then drying, compressing tablet process obtain electrode.
In above-mentioned preparation method, step(2)In also use dispersant, and stir or be ultrasonically treated, the dispersion
Agent is polyvinylpyrrolidone or hydroxylated cellulose.
In above-mentioned preparation method, step(2)The temperature of the drying process is 60 ~ 200 DEG C, and drying time 1 ~ 20 is small
When.
In above-mentioned preparation method, step(2)The temperature of the heat treatment is 300 ~ 700 DEG C, and the time is 10 ~ 200 points
Clock, the atmosphere used are inert gas(N2, Ar or He)Or go back Primordial Qi(N2/H2, Ar/H2).
In above-mentioned preparation method, prepared tree-shaped three-dimensional structure metal material its it is internal have apparent hole and
Channel;The grain size of electrode active material can be nanometer, micron or millimeter equidimension.
In above-mentioned preparation method, the electrode obtained carries out battery in the glove box with protective atmosphere(Including full electricity
Pond and half-cell etc.)Or the assembling of capacitor.The chemical property of both equipment is tested using corresponding equipment.
Compared with prior art, the present invention has the advantages that:
The method that the present invention prepares battery or electrode for capacitors using tree-shaped three-dimensional structure metal material as battery current collector,
This method can realize the direct-assembling of electrode active material, can also realize that electrode active material reacts in situ and prepare electricity
Pole.By the application of electrode to it is secondary can be in charge and discharge battery or capacitor, it will be apparent that improve the comprehensive performance of battery.This method will
Common metal conductor current collector is expanded into tree-shaped three-dimensional structure material, and electrode active material is effectively fixed on this
On material, realize that the method for not having to coating direct-assembling is prepared for stable positive and negative electrode.Equally, which is applied to
The electrode of battery or capacitor effectively increases the contact area of electrode active material and current collector, improve active material with
Electric conductivity between current collector, and effectively inhibit electrode active material caused structure in charge and discharge process to destroy and
The phenomenon that falling off, to realize its stable chemical property and improve the service life of energy storage system.
Description of the drawings
Fig. 1 is the flow chart entirely prepared;
Fig. 2 is tree-shaped three-dimensional structure copper product;
Fig. 3 is tree-shaped three-dimensional structure/MnO electrodes;
Fig. 4 is 100 mA g of tree-shaped three-dimensional structure/MnO electrodes-1Charge-discharge performance;
Fig. 5 is tree-shaped three-dimensional structure/MnO electrodes and copper foil/MnO electrode high rate performance variation diagrams;
Fig. 6 is tree-shaped three-dimensional structure/SnO2Electrode;
Fig. 7 is tree-shaped three-dimensional structure/SnO2200 mA g of electrode-1Charge-discharge performance and copper foil/SnO2100 mA g of electricity-1Become
Change figure.
Specific implementation mode
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do invention any type of limit
It is fixed.
Embodiment 1
Weigh 20g CuSO4·5H2O is dissolved completely in 200mL deionized waters, is slowly added to the 20mL concentrated sulfuric acids, magnetic agitation
It is down to room temperature to solution temperature, forms electrodeposit liquid.The disk that copper foil is cut into diameter 14mm is completely immersed in electricity as cathode
It deposits in liquid, by area 8cm2Copper sheet as anode also completely into electrodeposit liquid, between the electrode that 4cm is kept between the two poles of the earth
Away from.With 0.01A/cm2Current density carry out electro-deposition 60 s of plating in advance, then with 3 A/cm2Current density carry out electro-deposition
60 s of practical plating.Current collector after taking-up electro-deposition, is washed with deionized water remained on surface electrodeposit liquid, dries.Current collector is existed
The H of 5% volumetric concentration2/N2Under mixed atmosphere protection, it is warming up to 750 DEG C with the heating rate of 10 DEG C/min and carries out heat treatment 30min
Temperature fall afterwards obtains having tree-shaped three-dimensional structure copper product(See Fig. 2).Take manganese oxide(MnO)For battery active material, and will
Itself and conductive black obtain uniform solution by ultrasound and after being stirred in ethanol, and solution is assembled in the tree-shaped three-dimensional
Inside structure copper product, lithium ion cell electrode is obtained after heating(See Fig. 3).It is tested the result shows that prepared by the electrode
Battery is in 50mAg-1Under current density, discharge capacity reaches 1520 mAh g for the first time-1Reversible capacity is 1145, first library
Human relations efficiency is 75.02%(See Fig. 4).And the electrode has better high rate performance than the electrode directly coated with copper foil(See figure
5).
Embodiment 2
Weigh 30 g CuSO4·5H2O is dissolved completely in 200ml deionized waters, is slowly added to the 15 ml concentrated sulfuric acids, and magnetic force stirs
It mixes to solution temperature and is down to room temperature, form electrodeposit liquid.The disk that copper foil is cut into diameter 16mm, is completely immersed in as cathode
In electrodeposit liquid, by area 8cm2Copper sheet as anode also completely into the electricity for keeping 6 cm in electrodeposit liquid, between the two poles of the earth
Interpolar away from.With 0.03 A/cm2Current density carry out electro-deposition 90 s of plating in advance, then with 4 A/cm2Current density carry out
60 s of the practical plating of electro-deposition.Current collector after taking-up electro-deposition, is washed with deionized water remained on surface electrodeposit liquid, dries.It will collection
H of the stream device in 10% volumetric concentration2/N2Under mixed atmosphere protection, it is warming up to 650 DEG C with the heating rate of 8 DEG C/min and carries out hot place
50 min are managed, rear Temperature fall obtains having tree-shaped three-dimensional structure material.Take stannic oxide(SnO2)For battery active material,
And itself and conductive black are obtained into uniform solution by ultrasound and after being stirred in ethanol, solution is assembled in the three-dimensional
Material internal obtains lithium ion cell electrode after heating(See Fig. 6).It is tested the result shows that battery prepared by the electrode
In 200 mA g-1Under current density, discharge capacity reaches 1312 mAh g for the first time-1Reversible capacity is 1115 mAg-1, just
Secondary coulombic efficiency is 85%, and the electrode is than directly with the 100 mAh g of electrode of copper foil coating-1When performance it is more preferable(See figure
7).
Embodiment 3
Weigh 16g NiCl2·6H2O is dissolved completely in 200mL deionized waters, and 10g NH are added4Cl, magnetic agitation to solution
Temperature is down to room temperature, forms electrodeposit liquid.The disk that nickel foil is cut into diameter 16mm is completely immersed in electrodeposit liquid as cathode
In, by area 10cm2Nickel sheet as anode, and be completely immersed in electrodeposit liquid, between the electrode that 6cm is kept between the two poles of the earth
Away from.With 0.03A/cm2Current density carry out electro-deposition 50s be electroplated in advance, then with 2 A/cm2Current density carry out electro-deposition
20 s of practical plating.Current collector after taking-up electro-deposition, is washed with deionized water remained on surface electrodeposit liquid, dries.Current collector is existed
The H of 5% volumetric concentration2Under the protection of/Ar mixed atmospheres, it is warming up to 730 DEG C with the heating rate of 5 DEG C/min and is heat-treated
10min, rear Temperature fall obtain having tree-shaped three-dimensional structure material.Then as current collector, using graphene/sulphur as electrode
Active material, and active material and conductive black are obtained into uniform solution by ultrasound and after being stirred in ethanol, it will
Solution is assembled in inside the three-dimensional material, obtains lithium ion cell electrode.It is tested the result shows that battery prepared by the electrode
In 200 mA g-1Under current density, discharge capacity reaches 2160 mAh g for the first time-1Reversible capacity is 1760 mAg-1, for the first time
Coulombic efficiency be 81%, better than directly with copper foil coat electrode capacity.
Embodiment 4
Weigh 12g NiCl2·6H2O is dissolved completely in 200mL deionized waters, and 12 g NH are added4Cl, magnetic agitation is to molten
Liquid temperature is down to room temperature, forms electrodeposit liquid.The disk that nickel foam is cut into 19 mm of diameter is completely immersed in electricity as cathode
It deposits in liquid, by 15 cm of area2Nickel sheet as anode, and be completely immersed in electrodeposit liquid, keep 6cm's between the two poles of the earth
Electrode spacing.With 0.05A/cm2Current density carry out electro-deposition 50s be electroplated in advance, then with 3A/cm2Current density carry out electricity
30 s of the practical plating of deposition.Current collector after taking-up electro-deposition, is washed with deionized water remained on surface electrodeposit liquid, dries.By afflux
H of the device in 8% volumetric concentration2Under the protection of/Ar mixed atmospheres, it is warming up to 660 DEG C with the heating rate of 5 DEG C/min and is heat-treated
15 min, rear Temperature fall obtain having tree-shaped three-dimensional structure material.It takes graphene as electrode active material, and by it and leads
Electric carbon black obtains uniform solution by ultrasound and after being stirred in ethanol, and solution is assembled in the tree-shaped three-dimensional structure material
Material is internal, by heating electrode of super capacitor.Test itself the result shows that the electrode prepare capacitor in 1 A g-1Electric current
Under density, specific capacity reaches 152 F g-1, when electric current is increased to 100 A g-1When, the conservation rate of capacity is 53%.
Embodiment 5
Weigh 10g NiCl2·6H2O is dissolved completely in 200mL deionized waters, and 10g NH are added4Cl, magnetic agitation to solution
Temperature is down to room temperature, forms electrodeposit liquid.The disk that aluminium foil is cut into diameter 16mm is completely immersed in electrodeposit liquid as cathode
In, by 15 cm of area2Nickel sheet as anode, and be completely immersed in electrodeposit liquid, between the electrode that 6cm is kept between the two poles of the earth
Away from.With 0.2A/cm2Current density carry out electro-deposition 10 s of plating in advance, then with 3 A/cm2Current density carry out electro-deposition
50 s of practical plating.Material after taking-up electro-deposition, is washed with deionized water remained on surface electrodeposit liquid, dries.Three-dimensional material is existed
The H of 10% volumetric concentration2Under the protection of/Ar mixed atmospheres, it is warming up to 650 DEG C with the heating rate of 5 DEG C/min and is heat-treated
Temperature fall after 15min obtains having tree-shaped three-dimensional structure material.Graphene and manganese acetate is taken to be mixed into aqueous solution, and will be a small amount of
Solution is added in conductive black and polyvinylpyrrolidone, then obtains uniform solution by ultrasound and after being stirred, will be molten
Liquid is assembled in inside the three-dimensional material, then by drying and calcining to obtain graphene/MnO electrodes.It is tested the result shows that should
Electrode prepare battery in 200 mA g-1Under current density, discharge capacity reaches 1895 mAh g for the first time-1Reversible capacity
For 1468 mAg-1, first coulombic efficiency is 77.46 %, which is demonstrated by excellent chemical property.
Claims (10)
1. a kind of preparation method of tree-shaped three-dimensional structure metal material electrode, it is characterised in that include the following steps:(1)With metal
Conductor is substrate, and by the method for chemical deposition, tree-shaped three-dimensional structure metal material is grown on metallic conductor surface;(2)It will be electric
Pole active material by assembling or being grown directly upon the inside of tree-shaped three-dimensional structure metal material, after drying process tabletting obtain
Electrode.
2. preparation method according to claim 1, which is characterized in that step(1)The metallic conductor be copper foil, aluminium foil,
Nickel foil, foam copper, foamed aluminium or nickel foam.
3. preparation method according to claim 1, which is characterized in that step(1)After the chemical deposition, metal material is taken out
Material, is washed with deionized water remained on surface electrodeposit liquid, dries;Then it is heat-treated in a reducing atmosphere, reducing atmosphere is
The H of 2% ~ 10% volumetric concentration2/N2The H of gaseous mixture or 2% ~ 15% volumetric concentration2The temperature of/Ar gaseous mixtures, heat treatment is 500-
850℃。
4. preparation method as described in claim 1, which is characterized in that step(2)The electrode active material includes positive material
Material, negative material or capacitor electrode material;The positive electrode is LiMn2O4, cobalt acid lithium, lithium nickelate, cobalt nickel ion doped or phosphorus
Sour iron lithium;The negative material is carbon material, metal oxide, metal carbonate, metal sulfide, metal nitride, alloy
Heterojunction structure compound or silicon systems material;The capacitor electrode material is absorbent charcoal material, carbon gas gel electrode material, carbon are received
Mitron, activated carbon fibre, graphene, metal oxide materials or conducting polymer materials.
5. preparation method as described in claim 1, which is characterized in that step(2)The electrode active material complete to prepare and
After characterization, it is distributed in solvent and realizes assembling, electrode is obtained by tabletting;The solvent is water, ethyl alcohol, ether, acetone or nitrogen
Methyl pyrrolidone.
6. preparation method as described in claim 1, which is characterized in that step(2)Just divide after the electrode active material synthesis
It is dispersed in tree-shaped three-dimensional structure metal material, then drying, compressing tablet process obtain electrode.
7. preparation method as described in claim 1, which is characterized in that step(2)The reactant of the electrode active material exists
It is directly reacted in tree-shaped three-dimensional structure metal material, in situ to obtain electrode active material, then drying, compressing tablet process obtain
To electrode.
8. preparation method as described in claim 1, which is characterized in that step(2)In also use dispersant, and stir or super
Sonication, the dispersant are polyvinylpyrrolidone or hydroxylated cellulose.
9. preparation method as described in claim 1, which is characterized in that step(2)The temperature of the drying process is 60 ~ 200
DEG C, 1 ~ 20 hour drying time.
10. preparation method as described in claim 1, which is characterized in that step(2)The temperature of the heat treatment is 300 ~ 700
DEG C, the time is 10 ~ 200 minutes, and the atmosphere used is inert gas or goes back Primordial Qi.
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