CN109768224A - A kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery - Google Patents
A kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery Download PDFInfo
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- CN109768224A CN109768224A CN201910025744.1A CN201910025744A CN109768224A CN 109768224 A CN109768224 A CN 109768224A CN 201910025744 A CN201910025744 A CN 201910025744A CN 109768224 A CN109768224 A CN 109768224A
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- Prior art keywords
- copper foil
- acid nickel
- cobalt acid
- copper
- copper oxide
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 96
- 239000010941 cobalt Substances 0.000 title claims abstract description 96
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002253 acid Substances 0.000 title claims abstract description 94
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 56
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 155
- 239000011889 copper foil Substances 0.000 claims abstract description 142
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000840 electrochemical analysis Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 235000012149 noodles Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 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
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery, the pretreatment including copper foil, and the covering on one side to copper foil using copper foil tape;Then the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, obtains copper oxide/cobalt acid nickel nanowire composite;Growth in situ copper oxide/cobalt acid nickel nanowire composite piece is cut to the part of copper foil tape and copper foil adhesion with scissors;The long cobalt acid nickel nano wire copper foil of single side is cut out, obtain copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell, button cell is obtained by assembling and it is tested, the present invention by by the one side of copper foil flexibly can removal cover, only in the upper growth in situ cobalt acid nickel nano wire of copper foil one side, solves the problems, such as the electronics conduction between collector and battery case;By forming micro copper oxide, the performance of negative electrode of lithium ion battery is improved;Further improve specific capacity and high rate performance.
Description
Technical field
The present invention relates to battery material technical fields, especially a kind of to be based on growth in situ copper oxide/cobalt acid nickel nano wire
The preparation method of the negative electrode of lithium ion battery of composite material.
Background technique
Green high-capacity rechargeable battery of the lithium ion battery as a new generation is high with its voltage, energy density is big, cycle performance
Good, outstanding advantages of self discharge is small, memory-less effect, it is widely used in the electricity such as mobile phone, laptop, miniature camera
In device equipment, while before the fields such as electric car, satellite, space flight and aviation and Space Military also show good application
Scape and potential economic benefit.
Currently, have become new high-tech industry that this century is of great significance to national economy and people's lives it
One.Lithium ion battery possess higher energy density (210Wh/kg), higher operating voltage, lower self-discharge rate and preferably
Cycle life therefore occupy very important status in energy storage field, (such as capacity, energy is close for the performance of lithium ion battery
Degree, operating voltage, cycle performance, high rate performance etc.) it is related with the composition characteristic of positive and negative electrode material of lithium ion battery.Binary
Metal oxide cobalt acid nickel (NiCo2O4) due to its preferable electric conductivity and electro-chemical activity, and cobalt acid nickel theoretical specific capacity is
890mAhg-1 is 2.39 times of graphite, is showing unique advantage as lithium ion battery negative material.In recent years, scientific
Family the cobalt acid nickel with different structure and pattern is prepared for by different methods, to improve its performance, such as sea urchin shape, ball
Shape, flower-shaped and nano whiskers etc., useful to the stability of cobalt acid nickel very big raising.Studies have shown that on a current collector directly
Growth in situ cobalt acid nickel can shorten the diffusion length of electronics, alleviate the volume expansion in charge and discharge process, improve lithium-ion electric
The performance in pond.
For example, the Zhang Xiaogang seminar of Nanjing University is in paper Adv.Funct.Mater.2014,24,2630-2637
It discloses, long cobalt acid nickel nano wire matrix application greatly improves lithium ion in lithium ion battery negative material on carbon cloth
The performance of battery, in 0.5Ag-1Constant current charge-discharge point 100 encloses under current density, and specific capacity is also in 800mAhg-1More than, in 3Ag-1
The specific capacity of constant current charge-discharge is 4 times of cobalt acid nickel microballoon lithium ion battery negative material under current density.
But the research of long cobalt acid nickel material is typically all in foaming structure collector or carbon cloth on a current collector at present
Upper progress, long cobalt acid nickel material is also all to load on collector two sides on copper foil, can greatly influence in this way collector and
Electron transmission between battery case influences the performance of lithium ion battery.The long cobalt acid nickel of single side is relatively difficult on copper foil, just
Calculate that single side is long to have gone up cobalt acid nickel, Yao Gaowen be cobalt acid nickel at phase during, can direct quilt without the copper foil in Supported Co acid nickel face
Oxidation, forms the oxide of copper, equally will affect the electron transmission between collector and battery case, influence the property of lithium ion battery
Energy.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of compound based on growth in situ copper oxide/cobalt acid nickel nano wire
The another side of copper foil flexibly can be covered removably, effectively be prevented by the preparation method of the negative electrode of lithium ion battery of material, the present invention
The copper foil oxidation in not Supported Co acid nickel face is stopped, and the micro-oxidation copper in Supported Co acid nickel nano wire face can not only be contributed
Part specific capacity also has the effect cooperateed with cobalt acid nickel nano wire, greatly improves performance of lithium ion battery.
The technical solution of the present invention is as follows: it is a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium from
The preparation method of sub- battery cathode, comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, it is molten with hydrochloric acid
Liquid performs etching, and to remove the oxide components on copper foil surface, while is roughened copper foil surface, then with deionized water and
Ethyl alcohol cleans up the hydrochloric acid solution on copper foil, then in 60 DEG C of vacuum drying 8h;
S2), the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), molar ratio is the solvable of 1:2:10~100:1.5 by the long copper oxide of single side/cobalt acid nickel nano wire on copper foil
Property nickel salt, soluble cobalt, urea, cetyl trimethylammonium bromide be scattered in deionized water that stir 0.5~2h spare, will
Step S2) in the copper foil that covers be put into water heating kettle liner, copper foil tape downward, pours into stock solution, 100 DEG C~180 DEG C
5~10h is reacted, it is to be cooled to after room temperature, copper foil is taken out, is respectively cleaned 3 times with deionized water and ethyl alcohol;
S4), by the copper foil in step S3) dry 8 under conditions of temperature is 60 DEG C~for 24 hours, the use of temperature is then 300
DEG C Muffle furnace calcine 2h~6h, 1 DEG C/min~3 DEG C of heating rate/min obtain copper oxide/cobalt acid nickel nano wire composite wood
Material;
S5), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be obtained in step S4)
Growth in situ copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, thus
Obtain the long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, is aoxidized
Copper/cobalt acid nickel nanowire composite anode plate for lithium ionic cell;
S6), button cell is assembled, is worked with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell
Electrode, metal lithium sheet are put into diaphragm and separate working electrode and reference electrode as reference electrode and to electrode, instill electrolysis
Liquid enables battery to press closer with gasket and elastic slice, and assembling obtains button cell, and carries out electrification to assembled battery
Learn test.
Further, step S1) in, the copper foil with a thickness of 9 microns, the concentration of the hydrochloric acid of etching is 2M.
Further, step S2) in, the copper foil tape is High temperature-resistanadhesive adhesive tape.
Further, step S3) in, the soluble nickel salt is Ni (NO3)2·6H2O, nickel acetate, in nickel chloride
One or more mixing, the soluble cobalt are Co (NO3)2·6H2O, cobalt acetate, one or more of cobalt chloride
Mixing.
Further, step S5) in, obtained active material carrying capacity is 0.8mg~2.2mg.
Further, step S6) in, electrolyte needs the entire inside battery of complete wetting, and the electrolyte used is 1M
LiPF6。
Further, step S6) in, all assemblings carry out in the glove box with inert gas shielding, obtain knob
Battery is detained, the battery being completed need to stand 8-24h, using CR2030 type button cell as test carrier, test voltage range
For 0.01~3V.
The invention has the benefit that
1, the present invention by by the one side of copper foil flexibly can removal cover, only received in the upper growth in situ cobalt acid nickel of copper foil one side
Rice noodles solve the problems, such as the electronics conduction between collector and battery case;
2, the present invention will form micro copper oxide, can not only contribute few portion during high temperature makes cobalt acid nickel into phase
The specific capacity divided, can also act synergistically with cobalt acid nickel, improve copper oxide/cobalt acid nickel nanowire composite lithium ion jointly
The performance of battery cathode;
3, battery provided by the invention is in 100mAg-1It, can be with higher specific capacity in the long circulating test of current density
Circulation, stability is also relatively good, and the charge specific capacity to the 60th circle is still 1309.07mAhg-1, specific capacity and high rate performance are opposite
Prior art growth in situ cobalt acid nickel ion cathode material lithium has all obtained further raising.
Detailed description of the invention
Fig. 1 is the SEM figure of cobalt acid nickel carbon composite material prepared by the embodiment of the present invention 1;
Fig. 2 is the XRD diagram of cobalt acid nickel carbon composite material prepared by the embodiment of the present invention 1;
Fig. 3 is the constant current charge-discharge diagram of battery prepared by the embodiment of the present invention 1;
Fig. 4 is the high rate performance figure of battery prepared by the embodiment of the present invention 1;
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing:
Embodiment 1
A kind of preparation side based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery
Method, comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, be with concentration
The hydrochloric acid solution of 2M performs etching, and to remove the oxide components on copper foil surface, while is roughened copper foil surface, then uses
Deionized water and ethyl alcohol clean up the hydrochloric acid solution on copper foil, are then dried in vacuo 8h under the conditions of 60 DEG C of temperature;
S2), the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, by the soluble nickel salt Ni (NO of 0.4362g3)2·
6H2Co (the NO of O, 0.8731g3)2·6H2The urea of O, 0.3242g and the cetyl trimethylammonium bromide point of 0.1418g
Dissipate in deionized water stir 0.5h it is spare, the copper foil covered in step S2) is put into water heating kettle liner, copper foil tape court
Under, pour into stock solution, 150 DEG C of reaction 5h are to be cooled to after room temperature, and copper foil is taken out, respectively cleans 3 with deionized water and ethyl alcohol
Time;Dry 12h under conditions of temperature is 60 DEG C, the Muffle furnace calcining 3h for the use of temperature being then 300 DEG C, 2 DEG C of heating rate/
Min obtains copper oxide/cobalt acid nickel nanowire composite, copper oxide/cobalt acid nickel nanowire composite SEM figure of preparation
As shown in Figure 1, XRD diagram is as shown in Figure 2;
S4), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be obtained in step S3)
Growth in situ copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, thus
Obtain the long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, is aoxidized
Copper/cobalt acid nickel nanowire composite anode plate for lithium ionic cell;
S5), button cell is assembled, is worked with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell
Electrode, metal lithium sheet are put into diaphragm and separate working electrode and reference electrode as reference electrode and to electrode, instill 1M
LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolysis
Liquid enables battery to press closer with gasket and elastic slice, and using CR2030 type button cell as test carrier, all assemblings are equal
It is carried out in the glove box with inert gas shielding, obtains button cell;
S6), electro-chemical test will be carried out after assembled battery standing 8h, tests lithium ion battery 100mAg-1Length follow
Ring performance, test voltage range are 0.01~3V, and constant current charge-discharge cycle performance is as shown in figure 3, high rate performance is as shown in Figure 4.
Embodiment 2
A kind of preparation side based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery
Method, comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, be with concentration
The hydrochloric acid solution of 2M performs etching, and to remove the oxide components on copper foil surface, while is roughened copper foil surface, then uses
Deionized water and ethyl alcohol clean up the hydrochloric acid solution on copper foil, are then dried in vacuo 8h under the conditions of 60 DEG C of temperature;
S2), the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, by the soluble nickel salt Ni (NO of 0.2908g3)2·
6H2Co (the NO of O, 0.5821g3)2·6H2The urea of O, 0.2161g and the cetyl trimethylammonium bromide point of 0.0945g
Dissipate in deionized water stir 0.5h it is spare, the copper foil covered in step S2) is put into water heating kettle liner, copper foil tape court
Under, pour into stock solution, 150 DEG C of reaction 5h are to be cooled to after room temperature, and copper foil is taken out, respectively cleans 3 with deionized water and ethyl alcohol
Time;Dry 12h under conditions of temperature is 60 DEG C, the Muffle furnace calcining 3h for the use of temperature being then 300 DEG C, 2 DEG C of heating rate/
Min obtains copper oxide/cobalt acid nickel nanowire composite;
S4), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be obtained in step S3)
Growth in situ copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, thus
Obtain the long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, is aoxidized
Copper/cobalt acid nickel nanowire composite anode plate for lithium ionic cell;
S5), button cell is assembled, is worked with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell
Electrode, metal lithium sheet are put into diaphragm and separate working electrode and reference electrode as reference electrode and to electrode, instill 1M
LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolysis
Liquid enables battery to press closer with gasket and elastic slice, and using CR2030 type button cell as test carrier, all assemblings are equal
It is carried out in the glove box with inert gas shielding, obtains button cell;
S6), electro-chemical test will be carried out after assembled battery standing 8h, tests lithium ion battery 100mAg-1Length follow
Ring performance, test voltage range are 0.01~3V.
Embodiment 3
A kind of preparation side based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery
Method, comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, be with concentration
The hydrochloric acid solution of 2M performs etching, and to remove the oxide components on copper foil surface, while is roughened copper foil surface, then uses
Deionized water and ethyl alcohol clean up the hydrochloric acid solution on copper foil, are then dried in vacuo 8h under the conditions of 60 DEG C of temperature;
S2), the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, by the soluble nickel salt Ni (NO of 0.3635g3)2·
6H2Co (the NO of O, 0.7276g3)2·6H2The urea of O, 0.2702g and the cetyl trimethylammonium bromide point of 0.1182g
Dissipate in deionized water stir 0.5h it is spare, the copper foil covered in step S2) is put into water heating kettle liner, copper foil tape court
Under, pour into stock solution, 150 DEG C of reaction 5h are to be cooled to after room temperature, and copper foil is taken out, respectively cleans 3 with deionized water and ethyl alcohol
Time;Dry 12h under conditions of temperature is 60 DEG C, the Muffle furnace calcining 3h for the use of temperature being then 300 DEG C, 2 DEG C of heating rate/
Min obtains copper oxide/cobalt acid nickel nanowire composite;
S4), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be obtained in step S3)
Growth in situ copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, thus
Obtain the long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, is aoxidized
Copper/cobalt acid nickel nanowire composite anode plate for lithium ionic cell;
S5), button cell is assembled, is worked with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell
Electrode, metal lithium sheet are put into diaphragm and separate working electrode and reference electrode as reference electrode and to electrode, instill 1M
LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolysis
Liquid enables battery to press closer with gasket and elastic slice, and using CR2030 type button cell as test carrier, all assemblings are equal
It is carried out in the glove box with inert gas shielding, obtains button cell;
S6), electro-chemical test will be carried out after assembled battery standing 8h, tests lithium ion battery 100mAg-1Length follow
Ring performance, test voltage range are 0.01~3V.
Embodiment 4
A kind of preparation side based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery
Method, comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, be with concentration
The hydrochloric acid solution of 2M performs etching, and to remove the oxide components on copper foil surface, while is roughened copper foil surface, then uses
Deionized water and ethyl alcohol clean up the hydrochloric acid solution on copper foil, are then dried in vacuo 8h under the conditions of 60 DEG C of temperature;
S2), the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, by the soluble nickel salt Ni (NO of 0.5816g3)2·
6H2Co (the NO of O, 1.1624g3)2·6H2The urea of O, 0.4322g and the cetyl trimethylammonium bromide point of 0.1418g
Dissipate in deionized water stir 0.5h it is spare, the copper foil covered in step S2) is put into water heating kettle liner, copper foil tape court
Under, pour into stock solution, 150 DEG C of reaction 5h are to be cooled to after room temperature, and copper foil is taken out, respectively cleans 3 with deionized water and ethyl alcohol
Time;Dry 12h under conditions of temperature is 60 DEG C, the Muffle furnace calcining 3h for the use of temperature being then 300 DEG C, 2 DEG C of heating rate/
Min obtains copper oxide/cobalt acid nickel nanowire composite;
S4), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be obtained in step S3)
Growth in situ copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, thus
Obtain the long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, is aoxidized
Copper/cobalt acid nickel nanowire composite anode plate for lithium ionic cell;
S5), button cell is assembled, is worked with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell
Electrode, metal lithium sheet are put into diaphragm and separate working electrode and reference electrode as reference electrode and to electrode, instill 1M
LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolysis
Liquid enables battery to press closer with gasket and elastic slice, and using CR2030 type button cell as test carrier, all assemblings are equal
It is carried out in the glove box with inert gas shielding, obtains button cell;
S6), electro-chemical test will be carried out after assembled battery standing 8h, tests lithium ion battery 100mAg-1Length follow
Ring performance, test voltage range are 0.01~3V.
The above embodiments and description only illustrate the principle of the present invention and most preferred embodiment, is not departing from this
Under the premise of spirit and range, various changes and improvements may be made to the invention, these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (7)
1. a kind of preparation method based on growth in situ copper oxide/cobalt acid nickel nanowire composite negative electrode of lithium ion battery,
Characterized by comprising the following steps:
S1), copper foil pre-process, by copper foil cut out for the sizable circle of hydrothermal reaction kettle liner diameters, with hydrochloric acid solution into
Row etching, to remove the oxide components on copper foil surface, while is roughened copper foil surface, then uses deionized water and ethyl alcohol
The hydrochloric acid solution on copper foil is cleaned up, is then dried in vacuo 8h under conditions of temperature is 60 DEG C;
S2), wherein the covering on one side to copper foil using copper foil tape, copper foil tape is cut into and the copper in step S1)
The same size of foil is cut 0.3 centimetre or so of the blank sheet of paper outer ring that copper foil tape can glue face with scissors, and intermediate blank sheet of paper leaves,
So that step S1) in copper foil be unlikely to be fully adhered on copper foil tape, then copper foil is wiped clean with ethyl alcohol;
S3), the long copper oxide of single side/cobalt acid nickel nano wire on copper foil, the soluble nickel for being 1:2:10~100:1.5 by molar ratio
Salt, soluble cobalt, urea, cetyl trimethylammonium bromide be scattered in deionized water stir 0.5~2h it is spare, by step
S2 the copper foil covered in) is put into water heating kettle liner, and copper foil tape downward, pours into stock solution, 100 DEG C~180 DEG C reactions 5
~10h, it is to be cooled to after room temperature, copper foil is taken out, is respectively cleaned 3 times with deionized water and ethyl alcohol;
S4), by the copper foil in step S3) dry 8 under conditions of temperature is 60 DEG C~moved back for 24 hours to Muffle furnace, then by horse
Not furnace is warming up to 300 DEG C, and continues to calcine 2h~6h, and 1 DEG C/min~3 DEG C of heating rate/min obtain copper oxide/cobalt acid nickel and receive
Rice noodles composite material;
S5), copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell is prepared, it will be in situ obtained in step S4)
Growth copper oxide/cobalt acid nickel nanowire composite piece cuts the part of copper foil tape and copper foil adhesion with scissors, to obtain
The long cobalt acid nickel nano wire copper foil of single side;The long cobalt acid nickel nano wire copper foil of single side is cut into the disk of 12mm, obtains copper oxide/cobalt
Sour nickel nanowire composite anode plate for lithium ionic cell;
S6), button cell is assembled, is worked electrode with copper oxide/cobalt acid nickel nanowire composite anode plate for lithium ionic cell,
Metal lithium sheet is put into diaphragm and separates working electrode and reference electrode as reference electrode and to electrode, electrolyte is instilled, with pad
Piece and elastic slice enable battery to press closer, and assembling obtains button cell, and carries out electro-chemical test to assembled battery.
2. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S1) in, the copper foil with a thickness of 9 microns, the hydrochloric acid of etching it is dense
Degree is 2M.
3. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S2) in, the copper foil tape is High temperature-resistanadhesive adhesive tape.
4. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S3) in, the soluble nickel salt is Ni (NO3)2·6H2O, acetic acid
Nickel, one of nickel chloride or a variety of mixing, the soluble cobalt are Co (NO3)2·6H2O, cobalt acetate, in cobalt chloride
One or more of mixing.
5. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S5) in, obtained active material carrying capacity is 0.8mg~2.2mg.
6. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S6) in, electrolyte needs the entire inside battery of complete wetting, the electricity used
Solution liquid is 1M LiPF6.
7. according to claim 1 a kind of based on growth in situ copper oxide/cobalt acid nickel nanowire composite lithium ion
The preparation method of battery cathode, it is characterised in that: step S6) in, all assemblings are in the glove box with inert gas shielding
Middle progress, obtains button cell, and the battery being completed need to stand 8-24h, using CR2030 type button cell as test carrier,
Test voltage is 0.01~3V.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111453759A (en) * | 2020-03-25 | 2020-07-28 | 陕西科技大学 | Copper foil in-situ growth three-dimensional copper sulfide negative electrode material for sodium ion battery, and preparation method and application thereof |
CN115207278A (en) * | 2022-09-13 | 2022-10-18 | 深圳海润新能源科技有限公司 | Negative pole piece, preparation method thereof, battery and electric equipment |
CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014094181A1 (en) * | 2012-12-20 | 2014-06-26 | Zhongwei Chen | Bi-functional electrode for metal-air batteries and method for producing same |
CN104577052A (en) * | 2014-12-19 | 2015-04-29 | 浙江工业大学 | Electrochemical preparation method of polypyrrole/carbon fiber composite material electrode and application of polypyrrole/carbon fiber composite material electrode as positive electrode of lithium-ion battery |
CN105177535A (en) * | 2015-09-10 | 2015-12-23 | 安捷利(番禺)电子实业有限公司 | Manufacturing method of resistance copper foil |
CN106328944A (en) * | 2016-11-14 | 2017-01-11 | 南开大学 | Method for in-situ preparation of cathode indium antimonide of binder-free lithium/sodium-ion battery on copper foil surface |
CN107591251A (en) * | 2017-07-14 | 2018-01-16 | 电子科技大学 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
-
2019
- 2019-01-11 CN CN201910025744.1A patent/CN109768224B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014094181A1 (en) * | 2012-12-20 | 2014-06-26 | Zhongwei Chen | Bi-functional electrode for metal-air batteries and method for producing same |
CN104577052A (en) * | 2014-12-19 | 2015-04-29 | 浙江工业大学 | Electrochemical preparation method of polypyrrole/carbon fiber composite material electrode and application of polypyrrole/carbon fiber composite material electrode as positive electrode of lithium-ion battery |
CN105177535A (en) * | 2015-09-10 | 2015-12-23 | 安捷利(番禺)电子实业有限公司 | Manufacturing method of resistance copper foil |
CN106328944A (en) * | 2016-11-14 | 2017-01-11 | 南开大学 | Method for in-situ preparation of cathode indium antimonide of binder-free lithium/sodium-ion battery on copper foil surface |
CN107591251A (en) * | 2017-07-14 | 2018-01-16 | 电子科技大学 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
SHEN LAIFA ET AL.: "Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder-Free Flexible Electrodes for Energy Storage", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111453759A (en) * | 2020-03-25 | 2020-07-28 | 陕西科技大学 | Copper foil in-situ growth three-dimensional copper sulfide negative electrode material for sodium ion battery, and preparation method and application thereof |
CN115207278A (en) * | 2022-09-13 | 2022-10-18 | 深圳海润新能源科技有限公司 | Negative pole piece, preparation method thereof, battery and electric equipment |
US11670761B1 (en) | 2022-09-13 | 2023-06-06 | Shenzhen Hairun New Energy Technology Co., Ltd. | Negative electrode sheet and manufacturing method thereof and battery |
CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
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