CN110380023A - A kind of CNF-TMO lithium ion battery negative material and its preparation method and application - Google Patents
A kind of CNF-TMO lithium ion battery negative material and its preparation method and application Download PDFInfo
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- CN110380023A CN110380023A CN201910563764.4A CN201910563764A CN110380023A CN 110380023 A CN110380023 A CN 110380023A CN 201910563764 A CN201910563764 A CN 201910563764A CN 110380023 A CN110380023 A CN 110380023A
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- lithium ion
- ion battery
- transition metal
- spinning
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- -1 Transition metal salt Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940113088 dimethylacetamide Drugs 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000011017 operating method Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 230000005686 electrostatic field Effects 0.000 abstract 1
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- 239000007772 electrode material Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/625—Carbon or graphite
-
- 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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to field of lithium ion battery, a kind of CNF-TMO lithium ion battery negative material and its preparation method and application is disclosed.Transition metal salt is dissolved in organic solvent, polymer powder is added, so that it is sufficiently dissolved and is uniformly mixed, obtains spinning solution；By the way that spinning parameter is arranged, spinning is carried out under high voltage electrostatic field, obtains polymer-transition metal salt non-woven fabrics；It is soaked in the methanol solution of organic ligand again, using the strong coordination of transition metal ions and organic ligand, is formed uniformly one layer of organic metal framework material in polymeric fiber surface, obtains polymer-transition metal salt@organic metal framework material；Then it places it in tube furnace, so that it is carbonized at high temperature under hydrogen/argon gas mixed airflow, obtain carbon nano-fiber-transition metal, then by its thermal oxide in air, grind, obtain CNF-TMO lithium ion battery negative material.
Description
Technical field
The invention belongs to field of lithium ion battery, in particular to a kind of CNF-TMO lithium ion battery negative material and its system
Preparation Method and application.
Background technique
Lithium ion battery receives significant attention in recent years as the energy storage device with superior prospect.Meanwhile with new energy
The fast development of source automobile and intelligent portable equipment, mentions the energy storage device with higher reversible capacity and long circulation life
Urgent demand is gone out.However, commercial graphite electrode has lower theoretical capacity (372mAhg at present-1), be not able to satisfy as
The Battery Market demand of modern high-energy density and high power density.Transition metal oxide has more than conventional graphite electrodes because of it
High capacity and safety and there is very big potential using value.However, due to Li+Electrochemistry is anti-during insertion and deintercalation
It answers dynamics slowly and volume expansion is big, the practical application of transition metal oxide base negative electrode material is by very big obstruction.
Summary of the invention
In order to overcome shortcoming and deficiency existing in the prior art, the primary purpose of the present invention is that providing a kind of CNF-
The preparation method of TMO lithium ion battery negative material.
Another object of the present invention is to provide a kind of CNF-TMO lithium ion battery that above-mentioned preparation method is prepared
Negative electrode material；The active material has superior high rate performance and long circulating stability energy.
A further object of the present invention is to provide a kind of applications of above-mentioned CNF-TMO lithium ion battery negative material.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of CNF-TMO lithium ion battery negative material, including following operating procedure: by transition metal salt
Non-woven fabrics is obtained with mixed with polymers spinning, non-woven fabrics is soaked in the methanol solution of organic ligand, one layer of in-situ preparation
MOF；It is carbonized under the mixed atmosphere of hydrogen and argon gas again, is then aoxidized in air, is smashed and ground, CNF-TMO is made
Lithium ion battery negative material.
A kind of preparation method of above-mentioned CNF-TMO lithium ion battery negative material, specifically includes following operating procedure:
(1) transition metal salt is dissolved in organic solvent under magnetic agitation, polymer powder is added after being completely dissolved, stirs
It mixes for 24 hours, be uniformly mixed spinning solution；
(2) by blend spinning liquid in 10ml syringe, using stainless steel syringe needle, spinning parameter is set, carries out spinning；
60 DEG C of drying in an oven are removed after spinning, obtain polymer-transition metal salt (Polymer-TMS) non-woven fabrics；
(3) organic ligand is dissolved in methanol, then step (2) resulting polymers-transition metal salt non-woven fabrics is impregnated
In wherein, one layer of MOF is formed in fiber surface, is dried at 60 DEG C in an oven after taking-up, obtains polymer-transition metal salt@
Organic metal framework (Polymer-TMS@MOF) non-woven fabrics；
(4) polymer-transition metal salt@organic metal framework non-woven fabrics is placed in ceramic boat, is risen in tube furnace
Temperature is carbonized in hydrogen-argon-mixed body high temperature, obtains carbon nano-fiber-transition metal (CNF-TM)；Thermal oxide in air again,
It is cooled to room temperature, is pulverized, CNF-TMO lithium ion battery negative material (carbon nano-fiber-transition metal oxide is obtained
Active material).
Step (1) transition metal salt is nickel nitrate, nickel sulfate, copper nitrate, copper sulphate, cobalt nitrate, cobalt acetate, sulfuric acid
One or more of cobalt, zinc nitrate, zinc acetate, zinc sulfate and zinc chloride；The polymer is polyvinylpyrrolidone, polyethylene
Alcohol, polyacrylonitrile or polyethylene glycol oxide；The organic solvent is dimethylformamide, dimethyl acetamide or N- crassitude
Ketone；The mass ratio of the polymer and transition metal salt is 1:1~1:2.5；The solid content of polymer in the blend spinning liquid
It is 8%~15%.
Step (2) the stainless steel syringe needle internal diameter is 0.7mm~1.2mm；The spinning parameter are as follows: spinning spacing 16cm~
22mm, spinning voltage 11kV~20kV, syringe fltting speed 0.3ml/h~1.2ml/h, receive mode be roller receive or
Aluminium foil receives.
Step (3) organic ligand is one of trimesic acid, terephthalic acid (TPA), methylimidazole, benzimidazole
More than；The solution concentration that the organic ligand is dissolved in methanol formation is 0.05mol/L~0.15mol/L.
Step (4) the hydrogen-argon-mixed body includes the H of percentage by volume 5%2With the Ar of percentage by volume 95%.
The rate of step (4) described heating is 2 DEG C/min~5 DEG C/min.
The carburizing temperature of step (4) described high temperature cabonization is 500 DEG C~850 DEG C, and the time is 2~4h；The thermal oxide
Temperature is 250 DEG C~350 DEG C, and the time is 0.5h~3h.
A kind of application of the above-mentioned CNF-TMO lithium ion battery negative material in the negative electrode tab of production lithium ion battery.
The application be by CNF-TMO lithium ion battery negative material, conductive black (Super P), Kynoar (PVDF) according to
The ratio of mass ratio 7:2:1 is dissolved in N-Methyl pyrrolidone (NMP), is configured to slurry, is coated on copper foil, and drying is cut out
It is cut into the negative electrode tab for lithium ion battery.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) CNF-TMO lithium ion battery negative material prepared by the present invention, by by transition metal salt and polymer solution
Electrostatic spinning is mixed, being then immersed in the methanol solution of organic ligand makes fiber surface coat one layer of MOF, then in high temperature and hydrogen
It is carbonized and aoxidizes under argon-mixed atmosphere, obtain CNF-TMO material.So as to so that the size of transition metal oxide particle contracts
It is small to arrive nanoscale, and it is uniformly embedded into it among carbon nano-fiber derived from polymer.It, can due to the cladding of carbon material
Alleviate transition metal oxide particle well in Li+The volume expansion that insertion and deintercalation process occur, to improve battery
Long circulation life and the charge-discharge performance under high current, have good development prospect and application market.
(2) CNF-TMO lithium ion battery negative material prepared by the present invention has fibrous structure, takes connection between fiber and is
Electronics provides transportation route, effectively raises the efficiency of transmission of electronics or ion, is declined with capacity when reducing heavy-current discharge
Subtract, fiber surface thin carbon layer as derived from MOF can be further improved stability of material and electric conductivity, make material high rate performance and
Cycle performance to being obviously improved.
(3) present invention has preparation process simple, and equipment is easy to operate, and production cost is low, environment friendly and pollution-free, nonhazardous etc.
Feature, reaction temperature and time are easier to control, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is material SEM photograph prepared by embodiment 1, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 2 is material SEM photograph prepared by embodiment 2, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 3 is material SEM photograph prepared by embodiment 3, is followed successively by metal salt from left to right, from top to bottom and polymer is mixed
Spin fiber, the blend fibre with MOF and final electrode material.
Fig. 4 is the cycle performance test chart of material prepared by experimental example 1.
Fig. 5 is the cycle performance test chart of material prepared by experimental example 2.
Fig. 6 is the cycle performance test chart of material prepared by experimental example 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1:
(1) by 1g cobalt acetate (Co (Ac) under magnetic agitation2·4H2O it) is dissolved in 18g dimethyl acetamide (DMAc), it is complete
2g polyvinylpyrrolidone (PVP) powder is added after fully dissolved, for 24 hours, obtaining polyvinylpyrrolidone solid content is 9% for stirring
Uniform blend spinning liquid.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 20G, spinning parameter is set: being promoted
Speed 0.8ml/h, voltage 20kV, spinning distance 18cm, are received using roller, carry out spinning；It removes after spinning in baking oven
In 60 DEG C drying, obtain PVP-Co (Ac)2Non-woven fabrics, as metal salt and polyblend fibre.
(3) terephthalic acid (TPA) is dissolved in and forms the solution that concentration is 0.15mol/L in methanol, step (2) is obtained
PVP-Co(Ac)2Non-woven fabrics is soaked in wherein 12h, can be in fiber table due to the coordination of cobalt ions and terephthalic acid (TPA)
Face forms one layer of MOF, dries at 60 DEG C in an oven after taking-up, obtains PVP-Co (Ac)2@MOF non-woven fabrics, as with MOF
Blend fibre.
(4) by PVP-Co (Ac)2@MOF non-woven fabrics is placed in ceramic boat, according to the heating of 5 DEG C/min in tube furnace
Rate rises to 500 DEG C, in hydrogen-argon-mixed body (H25%/Ar 95%) high temperature carbonization, 4h is kept the temperature, CNF-Co fiber is obtained
Cloth；Obtained CNF-Co fiber is distributed in 250 DEG C of thermal oxides in air, 2h is kept the temperature, is cooled to room temperature, pulverizes, obtain most
Whole electrode material, as CNF-TMO lithium ion battery negative material.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 1.
By CNF-TMO lithium ion battery negative material, conductive black (Super P), Kynoar (PVDF) according to matter
It measures the ratio than 7:2:1 to be dissolved in N-Methyl pyrrolidone (NMP), is configured to slurry, is coated on copper foil, drying is cut
As electrode slice.
It uses lithium piece as anode, uses pole piece made from above-mentioned CNF-TMO as cathode, using 2400 diaphragm of Celgard,
Lithium ion battery is assembled using 2032 formula button cell structures, carries out charge-discharge test.With the current density of 1Ag-1 to compound
It is as shown in Figure 4 that material carries out cycle performance charge-discharge test.Composite material after 400 charge and discharge cycles capacity still keep
In 356mAh g-1High discharge capacity, illustrate the composite material have high capacity and stability.
Embodiment 2:
(1) by 1g nickel acetate (Ni (Ac) under magnetic agitation2·4H2) and 2g cobalt nitrate (Co (NO O3)2·6H2O it) is dissolved in
In 18g dimethyl acetamide (DMAc), 3.7g polyvinylpyrrolidone (PVP) powder is added after being completely dissolved, stirring for 24 hours, obtains
The uniform blend spinning liquid for being 15% to polyvinylpyrrolidone solid content.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 22G, spinning parameter is set: being promoted
Speed 0.6ml/h, voltage 19kV, spinning distance 20cm, are received using roller, carry out spinning；It removes after spinning in baking oven
In 60 DEG C drying, obtain PVP-Ni (Ac)2-Co(NO3)2Non-woven fabrics, as metal salt and polyblend fibre.
(3) terephthalic acid (TPA) is dissolved in and forms the solution that concentration is 0.05mol/L in methanol, step (2) is obtained
PVP-Ni(Ac)2-Co(NO3)2Non-woven fabrics is soaked in wherein 12h, can due to the coordination of nickel and cobalt ions and terephthalic acid (TPA)
To form one layer of MOF in fiber surface, is dried at 60 DEG C in an oven after taking-up, obtain PVP-Ni (Ac)2-Co(NO3)2@MOF
Non-woven fabrics, as with the blend fibre of MOF.
(4) by PVP-Ni (Ac)2-Co(NO3)2@MOF non-woven fabrics is placed in ceramic boat, in tube furnace according to 3 DEG C/
The heating rate of min rises to 850 DEG C, in hydrogen-argon-mixed body (H25%/Ar 95%) high temperature carbonization, 2h is kept the temperature, is obtained
CNF-Ni-Co fiber cloth；Obtained CNF-Ni-Co fiber is distributed in 350 DEG C of thermal oxides in air, 2h is kept the temperature, is cooled to room
Temperature is pulverized, and final electrode material, as CNF-TMO lithium ion battery negative material are obtained.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 2.
By CNF-TMO lithium ion battery negative material, conductive black (Super P), Kynoar (PVDF) according to matter
It measures the ratio than 7:2:1 to be dissolved in N-Methyl pyrrolidone (NMP), is configured to slurry, is coated on copper foil, drying is cut
As electrode slice.
It uses lithium piece as anode, uses pole piece made from above-mentioned CNF-TMO as cathode, using 2400 diaphragm of Celgard,
Lithium ion battery is assembled using 2032 formula button cell structures, carries out charge-discharge test.With the current density of 1Ag-1 to compound
It is as shown in Figure 5 that material carries out cycle performance charge-discharge test.Composite material after 480 charge and discharge cycles capacity still keep
In 364mAh g-1High discharge capacity, illustrate the composite material have high capacity and stability.
Embodiment 3:
(1) by 4g zinc acetate (Zn (Ac) under magnetic agitation2·4H2O it) is dissolved in 16g dimethyl acetamide (DMAc), it is complete
3g polyacrylonitrile (PAN) powder is added after fully dissolved, stirring for 24 hours, obtains the uniform mixing that polyacrylonitrile solid content is 13% and spins
Silk liquid.
(2) by blend spinning liquid in 10ml syringe, using the stainless steel syringe needle of 18G, spinning parameter is set: being promoted
Speed 1.2ml/h, voltage 14kV, spinning distance 22cm, are received using roller, carry out spinning；It removes after spinning in baking oven
In 60 DEG C drying, obtain PAN-Zn (Ac)2Non-woven fabrics, as metal salt and polyblend fibre.
(3) trimesic acid is dissolved in and forms the solution that concentration is 0.1mol/L, the PAN- that step (2) is obtained in methanol
Zn(Ac)2Non-woven fabrics is soaked in wherein 12h, due to the coordination of zinc ion and trimesic acid, can be formed in fiber surface
One layer of MOF dries at 60 DEG C in an oven after taking-up, obtains PAN-Zn (Ac)2@MOF non-woven fabrics, as with the blended of MOF
Fiber.
(4) by PAN-Zn (Ac)2@MOF non-woven fabrics is placed in ceramic boat, according to the heating of 2 DEG C/min in tube furnace
Rate rises to 650 DEG C, in hydrogen-argon-mixed body (H25%/Ar 95%) high temperature carbonization, 3h is kept the temperature, CNF-Co fiber is obtained
Cloth；Obtained CNF-Co fiber is distributed in 300 DEG C of thermal oxides in air, 0.5h is kept the temperature, is cooled to room temperature, pulverizes, obtain
Final electrode material, as CNF-TMO lithium ion battery negative material.
The SEM photograph of metal salt and polyblend fibre, the blend fibre with MOF and final electrode material is as schemed
Shown in 3.
By CNF-TMO lithium ion battery negative material, conductive black (Super P), Kynoar (PVDF) according to matter
It measures the ratio than 7:2:1 to be dissolved in N-Methyl pyrrolidone (NMP), is configured to slurry, is coated on copper foil, drying is cut
As electrode slice.
It uses lithium piece as anode, uses pole piece made from above-mentioned CNF-TMO as cathode, using 2400 diaphragm of Celgard,
Lithium ion battery is assembled using 2032 formula button cell structures, carries out charge-discharge test.With the current density of 1Ag-1 to compound
It is as shown in Figure 6 that material carries out cycle performance charge-discharge test.Composite material after 600 charge and discharge cycles capacity still keep
In 354mAh g-1High discharge capacity, illustrate the composite material have high capacity and stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of CNF-TMO lithium ion battery negative material, it is characterised in that including following operating procedure: incited somebody to action
It crosses metal salt and mixed with polymers spinning obtains non-woven fabrics, non-woven fabrics is soaked in the methanol solution of organic ligand, it is in situ raw
At one layer of MOF；It is carbonized under the mixed atmosphere of hydrogen and argon gas again, is then aoxidized in air, is smashed and ground, is made
CNF-TMO lithium ion battery negative material.
2. a kind of preparation method of CNF-TMO lithium ion battery negative material according to claim 1, it is characterised in that tool
Body includes following operating procedure:
(1) transition metal salt is dissolved in organic solvent under magnetic agitation, polymer powder is added after being completely dissolved, stirred
For 24 hours, be uniformly mixed spinning solution；
(2) by blend spinning liquid in 10ml syringe, using stainless steel syringe needle, spinning parameter is set, carries out spinning；Spinning
After remove in an oven 60 DEG C drying, obtain polymer-transition metal salt non-woven fabrics；
(3) organic ligand is dissolved in methanol, then step (2) resulting polymers-transition metal salt non-woven fabrics is soaked in it
In, one layer of MOF is formed in fiber surface, is dried at 60 DEG C in an oven after taking-up, it is organic to obtain polymer-transition metal salt@
Metal framework non-woven fabrics；
(4) polymer-transition metal salt@organic metal framework non-woven fabrics is placed in ceramic boat, is heated up in tube furnace,
Hydrogen-argon-mixed body high temperature carbonization, obtains carbon nano-fiber-transition metal；Thermal oxide in air again, is cooled to room temperature, grinds
Grinds obtain CNF-TMO lithium ion battery negative material.
3. preparation method according to claim 2, it is characterised in that: step (1) transition metal salt is nickel nitrate, sulphur
One of sour nickel, copper nitrate, copper sulphate, cobalt nitrate, cobalt acetate, cobaltous sulfate, zinc nitrate, zinc acetate, zinc sulfate and zinc chloride
And more than one；The polymer is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile or polyethylene glycol oxide；It is described organic
Solvent is dimethylformamide, dimethyl acetamide or N-Methyl pyrrolidone；The quality of the polymer and transition metal salt
Than for 1:1~1:2.5；The solid content of polymer is 8%~15% in the blend spinning liquid.
4. preparation method according to claim 2, it is characterised in that: step (2) the stainless steel syringe needle internal diameter is 0.7mm
~1.2mm；The spinning parameter are as follows: spinning spacing 16cm~22mm, spinning voltage 11kV~20kV, syringe fltting speed
0.3ml/h~1.2ml/h, the mode that receives are that roller receives or aluminium foil receives.
5. preparation method according to claim 2, it is characterised in that: step (3) organic ligand is trimesic acid, right
One or more of phthalic acid, methylimidazole, benzimidazole；The organic ligand is dissolved in the solution concentration of methanol formation
For 0.05mol/L~0.15mol/L.
6. preparation method according to claim 2, it is characterised in that: step (4) the hydrogen-argon-mixed body includes volume
The H of percentage 5%2With the Ar of percentage by volume 95%.
7. preparation method according to claim 2, it is characterised in that: the rate of step (4) described heating be 2 DEG C/min~
5℃/min。
8. preparation method according to claim 2, it is characterised in that: the carburizing temperature of step (4) described high temperature cabonization is
500 DEG C~850 DEG C, the time is 2~4h；The temperature of the thermal oxide is 250 DEG C~350 DEG C, and the time is 0.5h~3h.
9. a kind of CNF-TMO lithium ion battery negative material according to claim 1 or 2 is negative production lithium ion battery
Application in pole piece.
10. application according to claim 9, it is characterised in that: the application is by CNF-TMO negative electrode of lithium ion battery material
Material, conductive black, Kynoar are dissolved in N-Methyl pyrrolidone according to the ratio of mass ratio 7:2:1, are configured to slurry,
It is coated on copper foil, drying cuts the negative electrode tab for becoming lithium ion battery.
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