CN106099106A - Ultrafast fill lithium ion battery negative material, its preparation method and lithium ion battery - Google Patents
Ultrafast fill lithium ion battery negative material, its preparation method and lithium ion battery Download PDFInfo
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- CN106099106A CN106099106A CN201610705609.8A CN201610705609A CN106099106A CN 106099106 A CN106099106 A CN 106099106A CN 201610705609 A CN201610705609 A CN 201610705609A CN 106099106 A CN106099106 A CN 106099106A
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- Prior art keywords
- lithium ion
- ion battery
- negative material
- preparation
- battery negative
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- 239000000463 material Substances 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 229910016283 MxNyOz Inorganic materials 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 238000011049 filling Methods 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000002073 nanorod Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002088 nanocapsule Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 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
- 238000004891 communication Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 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
- H01M4/58—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on 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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a kind of ultrafast lithium ion battery negative material, its preparation method and lithium ion battery of filling, concrete preparation method is, uses metal-oxide MxNyOz(M, N=Zn, Cu, Fe, Mn, Ge, Co, Ni, Ti, V, Cr, Cd, Sn etc., 0≤x≤3;0≤y≤3;1≤z≤5) nanometer rods is template, with itrogenous organic substance in-situ polymerization, presoma is obtained after carbonization, presoma is added stripper plate reagent, the meso-porous hollow bar-shaped carbon Nano capsule negative material of N doping is obtained after process, compared with doing lithium ion battery with existing material with carbon element, under lasting high current density, ultrafast discharge and recharge can be realized simultaneously and capacity is high, cycle life overlength.After 10A/g electric current density discharge and recharge, circulation 10,000 circle, capacity is stably held in 370mA h/g;After 30A/g excess current densities discharge and recharge, circulation 10,000 circle, capacity is still stably held in 290mA h/g, has fabulous cyclical stability and high power capacity, and preparation method is simple, it is not necessary to complex device, can be prepared on a large scale, be suitable to commercial production.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of ultrafast fill lithium ion battery negative material, its
Preparation method and lithium ion battery.
Background technology
Developing rapidly of portable communication apparatus, urgent needs high power density, high capacity density, have extended cycle life, can
The lithium ion battery of ultrafast discharge and recharge.Material with carbon element enrich, low cost, can avoid when doing lithium ion battery negative because of use silicon, stannum,
Metal-oxides etc. do the enormousness expansion issues that negative material causes, and are especially suitable for as lithium ion battery negative material.
But, the most business-like lithium ion battery with graphite as negative material, its theoretical specific capacity is on the low side (372mAh/g), restriction
The raising of lithium ion battery capacity, it is impossible to meet following high power capacity, the demand of long-life electron equipment, current alternative graphite
New Type of Carbon negative material obtain the research of increasing scholar.The carbon of N doping, as negative material, can reach high filling
Discharge-rate, but under lasting high current density discharge and recharge, there is the problem that capacity is on the low side, cycle life is short, it is impossible to meet
High power density, high capacity density, have extended cycle life and can super-quick charging electric discharge demand.
Summary of the invention
The purpose of the present invention be contemplated to solve the problems referred to above and provide a kind of ultrafast fill, high power capacity, extra long life performance
Lithium ion battery negative material, its preparation method and lithium ion battery.
The purpose of the present invention is achieved through the following technical solutions:
A kind of ultrafast fill, the preparation method of the lithium ion battery negative material of high power capacity, extra long life performance, specifically include
Following steps:
(1) use metal oxide nanorods as template, metal oxide nanorods is distributed in solution;
(2) in the solution of step (1), add itrogenous organic substance and buffer, itrogenous organic substance is received with metal-oxide
Rice rod carries out in-situ polymerization;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbon in nitrogen or ar gas environment
Change, obtain presoma;
(4) presoma step (3) obtained adds stripper plate reagent, is centrifuged, cleans, dries, i.e. obtain lithium after process
Ion battery cathode material.
The molecular formula of the metal oxide nanorods described in step (1) is MxNyOz, wherein M, N=Zn, Cu, Fe, Mn, Ge,
Co, Ni, Ti, V, Cr, Cd or Sn, 0≤x≤3;0≤y≤3;1≤z≤5.
Preferably, described metal oxide nanorods be selected from zinc oxide, ferrum oxide, manganese oxide, germanium oxide, copper germanate,
Zinc or the one of zinc germanate.
Preferably, a length of 200-2000nm of the metal oxide nanorods described in step (1), external diameter is 10-
500nm, described solution is ethanol water, and more than metal oxide nanorods, the mass ratio of ethanol water is 1:200-250.
Preferably, the itrogenous organic substance described in step (2) is selected from dopamine, dopamine hydrochloride, polyurethane, pyrroles, hydramine
Or the one of nitrate, described buffer is trishydroxymethylaminomethane, described metal oxide nanorods and nitrogenous have
The mass ratio of machine thing is 1:0.2-5, and metal oxide nanorods is 2-5:1 with the mass ratio of buffer.
Preferably, the temperature of the in-situ polymerization described in step (2) is 20-25 DEG C, and the time is 10-30h.
Preferably, the temperature of the carbonization described in step (3) is 400-900 DEG C, and the time is 4-12h.
Preferably, the one in hydrochloric acid, sulphuric acid, nitric acid, acetic acid or carbonic acid of the stripper plate reagent described in step (4) or
Multiple mixture, the time of stripper plate agent treated is 1h-7 days, more preferably 1-3 days, most preferably 2.5 days.
A kind of lithium ion battery negative material, described lithium ion battery negative material uses above-mentioned preparation method system
?.
A kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described negative pole uses above-mentioned lithium ion
Cell negative electrode material prepares.
Preparing lithium ion battery uses usual technological means to prepare, and concretely comprises the following steps:
(1) lithium ion battery negative material, binding agent and conductive agent are mixed, add dispersant furnishing slurry, coating
On Copper Foil, after vacuum dried, roll-in, prepare into negative plate;
(2) prepared negative plate is assembled with positive pole lithium sheet, barrier film and electrolyte, i.e. prepare lithium ion battery.
Above-mentioned binding agent is polyvinyladine floride (PVDF), and conductive agent is Super-P, and dispersant is N-Methyl pyrrolidone
(NMP), lithium ion battery negative material and binding agent polyvinyladine floride (PVDF), conductive agent Super-P are according to the weight of 8:1:1
Than mixing;
Above-mentioned positive pole uses lithium sheet;Barrier film uses microporous polypropylene membrane;Electrolyte uses ethylene carbonate (EC), carbonic acid
Dimethyl ester (DMC) and the mixed liquor of Ethyl methyl carbonate (EMC), use the LiPF of 1mol/L6Three component mixed solvents, wherein
The mass ratio of EC, DMC and EMC is 1:1:1.
Compared with prior art, the present invention uses metal oxide nanorods as template, and nanometer rods can be adjusted flexibly
Size, obtains the electrode material that series length is different with external diameter, finally prepares the meso-porous hollow bar-shaped carbon Nano capsule of N doping
Negative material.Using in the nitrogen component that the method produces, pyrroles's nitrogen (N-5) and pyridine nitrogen (N-6) content ratio are high, by introducing
Super a high proportion of N-5 and N-6, creates substantial amounts of edge and surface " cavity " defect sites, adds the specific capacity of material, again
Create loose structure, further enhancing the chemical property of material;The N-Q of the low low content of graphite nitrogen (N-Q) content ratio
Be conducive to maintaining the stability of structure, the negative material additionally prepared to have the bar-shaped capsule structure of closing meso-porous hollow of uniqueness, tool
There is good mechanical stability, N-5 and the N-6 doping of high-load and the synergism of mesoporous space bar-shaped capsule unique texture,
The volumetric expansion in charge and discharge process of this negative material be can effectively suppress, electron conduction and specific capacity improved, and the biggest
Under electric current density, it is achieved ultrafast discharge and recharge and capacity are high, have extended cycle life.
Use the lithium ion battery that lithium ion battery negative material of the present invention prepares, charge and discharge under 10A/g high current density
Electricity, after circulation 10000 circle, capacity is stably held in about 370, discharge and recharge under 30A/g excess current densities, circulation 10000 circle
Rear capacity is stably held in about 290, has fabulous cyclical stability and high power capacity.Additionally, preparation method of the present invention is simple,
Need not complex device, can be prepared on a large scale, be suitable to commercial production.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, and certainly, the accompanying drawing in below describing is only the present invention's
Embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to provide
Accompanying drawing obtains other accompanying drawing.
Fig. 1 is the TEM figure of negative material of the present invention;
Fig. 2 is the graceful spectrogram of negative material of the present invention;
Fig. 3 is the N1s XPS figure of negative material of the present invention;
Fig. 4 is lithium ion battery charge and discharge cycles curve when electric current density is 10A/g;
Fig. 5 is lithium ion battery charge and discharge cycles curve when electric current density is 30A/g.
Detailed description of the invention
In order to further illustrate the present invention, the one that provides the present invention below in conjunction with embodiment is ultrafast fills, high power capacity, super
Long-life performance lithium ion battery negative material, its preparation method and lithium ion battery are described in detail, but can not be managed
Solve as limiting the scope of the present invention.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Being 480nm by average length, external diameter is the zinc germanate nanometer rods template of 65nm, weighs 0.15g, is distributed to 20ml second
In the mixed solution of alcohol and 15ml water, and weigh dopamine hydrochloride 0.23g, add in above-mentioned solution, be subsequently adding 0.05g tri-
(methylol) aminomethane and 10ml water, after being stirred at room temperature 20h.After being centrifuged, cleaning, dry, pipe put into by the sample after drying
In formula stove, first it is passed through argon and gets rid of air, be continually fed into argon, be then warmed up to 550 DEG C, carbonization 4h, finally cool down with stove
Sample to room temperature, obtain presoma.Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day, centrifugal, clear
Wash, dry, obtain lithium ion battery negative material.
Anticathode material carries out transmission electron microscope detection, as it is shown in figure 1, as seen from Figure 1, negative material is hollow to result
Bar-shaped capsule structure, average length is 500nm, and mean outside diameter is 80nm;Fig. 2 is the Raman spectrogram of negative material, can by Fig. 2
To find out ID/IG=2.04, show that material with carbon element has a lot of defect, these " cavity " defect sites, add the specific volume of material
Amount, enhances the chemical property of material, and Fig. 3 is the XPS figure of the N1S of negative material, and as seen from Figure 3, the present embodiment is born
In the material of pole, the nitrogen of doping exists with pyrroles's nitrogen (N-5), pyridine nitrogen (N-6), three kinds of forms of graphite nitrogen (N-Q), and wherein three contains
Amount percentage ratio is: 34:43:23.
The lithium ion battery negative material that the present embodiment is obtained and binding agent polyvinyladine floride (PVDF), conductive agent
Super-P mixes according to the weight ratio of 8:1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, painting
Overlay on Copper Foil, and vacuum dried, roll-in, it is prepared as negative plate.Positive pole uses lithium sheet, and barrier film uses microporous polypropylene membrane,
Use the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and Ethyl methyl carbonate (EMC) as electrolyte, mass ratio
For 1:1:1, use the LiPF of 1mol/L6Three component mixed solvents as electrolyte, microporous polypropylene membrane is barrier film, by negative pole
Sheet, positive plate, barrier film and electrolyte are assembled into CR2016 simulated battery.
The electric current using 10A/g, 30A/g carries out constant current charge-discharge experiment, and (wherein the electric current density of first lap is 400mA/
G), the cycle performance of the lithium ion battery that test prepares, charging/discharging voltage is limited in 0.01-3V, uses Shenzhen's new Weir electricity
The chemical property of the Neware CT-3008 battery test system test battery of sub-company limited, tests at room temperature condition, Fig. 4
For being charge and discharge cycles curve during 10A/g, as shown in Figure 4, discharge and recharge under 10A/g high current density in electric current density, follow
Ring 10, after 000 circle, capacity is stably held in 370, has good cyclical stability and high power capacity.Fig. 5 is in electric current density to be
Charge and discharge cycles curve during 30A/g, as shown in Figure 5, discharge and recharge under 30A/g excess current densities, after circulation 10,000 circle
Capacity is stably held in 290, has fabulous cyclical stability and high power capacity.
Embodiment 2
It is 480nm by average length, the zinc germanate nanometer rods template of a diameter of 65nm, weigh weight 0.15g, be distributed to
In the mixed solution of 20mL ethanol and 15mL water, and weigh dopamine hydrochloride 0.075g, add in above-mentioned solution, be subsequently adding
0.05g tri-(methylol) aminomethane, and 10mL water, after after 20h is stirred at room temperature, being centrifuged, cleaning, dry, the sample after drying
Product are put in tube furnace, are first passed through argon and get rid of air, are continually fed into argon, are then warmed up to 550 DEG C, carbonization 4h.Finally with
Stove samples after being cooled to room temperature, obtains presoma;Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day,
Centrifugal, cleaning, drying, obtain negative material.
By the lithium ion battery negative material that obtains with the inclined fluorine ethylene of binding agent (PVDF), conductive agent Super-P according to 8:
The weight ratio mixing of 1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, is coated on Copper Foil, and
Vacuum dried, roll-in, is prepared as negative plate;Positive pole uses lithium sheet, uses the LiPF of 1mol/L6Three component mixed solvent EC
: DMC: EMC=1:1:1 liquid is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into CR2016 simulated battery, and gained battery exists
Discharge and recharge under the high current density of 10A/g, after circulation 10000 circle, capacity is stably held in about 320;Big electric current at 30A/g
Discharge and recharge under density, after circulation 10,000 circle, capacity is stably held in 250mA about h/g.
Embodiment 3
It is 900nm by average length, the copper germanate nanometer rods template of a diameter of 40nm, weigh weight 0.15g, be distributed to
In the mixed solution of 20mL ethanol and 15mL water, and weigh dopamine hydrochloride 0.23g, add in above-mentioned solution, be subsequently adding
0.05g tri-(methylol) aminomethane, and 10mL water, after 20h is stirred at room temperature, centrifugal, clean, the sample after drying, after drying
Product are put in tube furnace, are first passed through argon and get rid of air, are continually fed into argon, are then warmed up to 550 DEG C, carbonization 4h.Finally with
Stove samples after being cooled to room temperature, obtains presoma;Then weigh 0.2g presoma to be soaked in 80mL chloroazotic acid, after standing 1 day,
Centrifugal, cleaning, drying, obtain negative material.
The lithium ion battery negative material that the present embodiment is obtained and the inclined fluorine ethylene of binding agent (PVDF), conductive agent Super-
P mixes according to the weight ratio of 8:1:1, adds appropriate N-Methyl pyrrolidone (NMP) as dispersant furnishing slurry, is coated in copper
On paper tinsel and vacuum dried, roll-in, is prepared as negative plate;Positive pole uses lithium sheet, uses the LiPF of 1mol/L6Three components mix
Bonding solvent EC: DMC: EMC=1:1:1 liquid is electrolyte, and microporous polypropylene membrane is barrier film, is assembled into CR2016 simulated battery.Institute
Obtaining battery discharge and recharge under 10A/g high current density, after circulation 10,000 circle, capacity is stably held in 300mA about h/g,
Discharge and recharge under 30A/g high current density, after circulation 10,000 circle, capacity is stably held in 210mA about h/g.
Embodiment 4
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using zinc oxide nano rod as template, a length of 200nm of zinc oxide nano rod, external diameter is 10nm, by 1g
Zinc oxide nano rod is distributed in 200g ethanol water;
(2) dopamine and the 0.2g trishydroxymethylaminomethane of 0.1g are added in the solution, by dopamine and zinc oxide nano
Rice rod carries out in-situ polymerization, stirs 10h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in ar gas environment, obtain
Presoma, the temperature of carbonization is 400 DEG C, and the time is 12h;
(4) presoma step (3) obtained adds process 1h in sulphuric acid, is centrifuged, cleans, dries, i.e. obtain after process
Lithium ion battery negative material.
Embodiment 5
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using zinc germanate nanometer rods is 200nm as template, a length of 1000nm of zinc germanate nanometer rods, external diameter, will
1g zinc germanate nanometer rods is distributed in 230g ethanol water;
(2) polyurethane and the 0.4g trishydroxymethylaminomethane of 5g are added in the solution, by polyurethane and zinc germanate nanometer
Rod carries out in-situ polymerization, stirs 20h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in ar gas environment, obtain
Presoma, the temperature of carbonization is 600 DEG C, and the time is 8h;
(4) presoma step (3) obtained adds process 2.5 days in hydrochloric acid, is centrifuged, cleans, dries, to obtain final product after process
To lithium ion battery negative material.
Embodiment 6
A kind of lithium ion battery negative material, uses following methods to prepare:
(1) using ferric oxide nano rod is 500nm as template, a length of 2000nm of ferric oxide nano rod, external diameter, will
1g ferric oxide nano rod is distributed in 250g ethanol water;
(2) add pyrroles and the 0.5g trishydroxymethylaminomethane of 10g in the solution, pyrroles is entered with ferric oxide nano rod
Row in-situ polymerization, stirs 30h under room temperature;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in nitrogen environment, obtain
Presoma, the temperature of carbonization is 900 DEG C, and the time is 4h;
(4) presoma step (3) obtained adds process 7 days in nitric acid, is centrifuged, cleans, dries, i.e. obtain after process
Lithium ion battery negative material.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the ultrafast preparation method filling lithium ion battery negative material, it is characterised in that specifically include following steps:
(1) use metal oxide nanorods as template, metal oxide nanorods is distributed in solution;
(2) in the solution of step (1), itrogenous organic substance and buffer are added, by itrogenous organic substance and metal oxide nanorods
Carry out in-situ polymerization;
(3) after the solids in step (2) mixed solution being centrifuged, cleaning, dry, carbonization in nitrogen or ar gas environment,
To presoma;
(4) presoma step (3) obtained adds stripper plate reagent, is centrifuged, cleans, dries, i.e. obtain lithium ion after process
Cell negative electrode material.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (1)
The molecular formula of described metal oxide nanorods is MxNyOz, wherein M, N=Zn, Cu, Fe, Mn, Ge, Co, Ni, Ti, V, Cr,
Cd or Sn, 0≤x≤3;0≤y≤3;1≤z≤5.
The preparation method of a kind of lithium ion battery negative material the most according to claim 2, it is characterised in that described gold
Belong to oxide nano-rod selected from zinc oxide, ferrum oxide, manganese oxide, germanium oxide, copper germanate, zinc or the one of zinc germanate.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (1)
The a length of 200-2000nm of described metal oxide nanorods, external diameter is 10-500nm, and described solution is that ethanol is water-soluble
Liquid, metal oxide nanorods is 1:200-250 with the mass ratio of ethanol water.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (2)
Described itrogenous organic substance is selected from dopamine, dopamine hydrochloride, polyurethane, pyrroles, hydramine or the one of nitrate, and described is slow
Rushing liquid is trishydroxymethylaminomethane, and metal oxide nanorods is 1:0.2-5 with the mass ratio of itrogenous organic substance, burning
Thing nanometer rods is 2-5:1 with the mass ratio of buffer.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (2)
The temperature of described in-situ polymerization is 20-25 DEG C, and the time is 10-30h.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (3)
The temperature of described carbonization is 400-900 DEG C, and the time is 4-12h.
The preparation method of a kind of lithium ion battery negative material the most according to claim 1, it is characterised in that step (4)
Described stripper plate reagent one or more mixture in hydrochloric acid, sulphuric acid, nitric acid, acetic acid or carbonic acid, stripper plate reagent
The time processed is 1h-7 days.
9. one kind ultrafast is filled lithium ion battery negative material, it is characterised in that described lithium ion battery negative material uses power
Profit requires that the preparation method described in 1-8 any one prepares.
10. a lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that described negative pole uses power
Profit requires that the lithium ion battery negative material described in 9 prepares.
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