CN109768224B - Preparation method of lithium ion battery cathode based on in-situ growth of copper oxide/nickel cobaltate nanowire composite material - Google Patents
Preparation method of lithium ion battery cathode based on in-situ growth of copper oxide/nickel cobaltate nanowire composite material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000002070 nanowire Substances 0.000 title claims abstract description 73
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 61
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 61
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 149
- 239000011889 copper foil Substances 0.000 claims abstract description 149
- 239000002390 adhesive tape Substances 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 238000005520 cutting process Methods 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010008 shearing Methods 0.000 claims abstract description 7
- 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
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000840 electrochemical analysis Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 238000011068 loading method Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 abstract 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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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- 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 invention provides a preparation method of a lithium ion battery cathode based on an in-situ grown copper oxide/nickel cobaltate nanowire composite material, which comprises the steps of preprocessing a copper foil, and covering one surface of the copper foil by using a copper foil adhesive tape; then growing the copper oxide/nickel cobaltate nanowire on one surface of the copper foil to obtain a copper oxide/nickel cobaltate nanowire composite material; shearing the copper foil adhesive tape and the part of the copper foil which is adhered by the copper foil by using scissors to obtain the in-situ grown copper oxide/nickel cobaltate nanowire composite material sheet; the method comprises the following steps of cutting a single-sided long nickel cobaltate nanowire copper foil to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate, assembling to obtain a button battery, and testing the button battery; the performance of the negative electrode of the lithium ion battery is improved by forming a trace amount of copper oxide; further improving the specific capacity and rate capability.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method of a lithium ion battery cathode based on an in-situ growth copper oxide/nickel cobaltate nanowire composite material.
Background
The lithium ion battery is used as a new generation of green high-energy rechargeable battery, has the outstanding advantages of high voltage, high energy density, good cycle performance, small self-discharge, no memory effect and the like, is widely applied to electrical equipment such as mobile phones, notebook computers, small cameras and the like, and simultaneously shows good application prospect and potential economic benefit in the fields of electric automobiles, satellites, aerospace, space military and the like.
At present, the method becomes one of high-tech industries which have important significance to national economy and people's life in the century. The lithium ion battery has higher energy density (210Wh/kg), higher working voltage, lower self-discharge rate and better cycle life, so the lithium ion battery plays a very important role in the field of energy storage, and the performance (such as capacity, energy density, working voltage, cycle performance, rate performance and the like) of the lithium ion battery is related to the characteristics of the positive and negative electrode materials of the lithium ion battery. Binary metal oxide nickel cobaltate (NiCo)2O4) Because the nickel cobaltate has better conductivity and electrochemical activity, and the theoretical specific capacity of the nickel cobaltate is 890mAhg < -1 >, which is 2.39 times of that of graphite, the nickel cobaltate has unique advantages when being used as a negative electrode material of a lithium ion battery. In recent years, scientists have prepared nickel cobaltate with different structures and morphologies by different methods to improve the performance of nickel cobaltate, such as sea urchin-shaped, spherical, flower-shaped, nano needle-shaped and the like, and the stability of nickel cobaltate is greatly improved. Research shows that the nickel cobaltate directly grows on the current collector in situ, the diffusion distance of electrons can be shortened, the volume expansion in the charge and discharge process is relieved, and the performance of the lithium ion battery is improved.
For example, Zhang Xiao just topic group of Nanjing university in the papers adv.Funct.Mater.2014,24, 2630--1Constant current charge and discharge point 1 under current density00 circles, specific capacity of 800mAhg-1Above, in 3Ag-1The specific capacity of constant-current charging and discharging under the current density is 4 times of that of the nickel cobaltate microsphere lithium ion battery cathode material.
However, at present, the research on the nickel cobaltate material on the current collector is generally performed on the current collector with a foam structure or carbon cloth, and the nickel cobaltate material on the copper foil is also loaded on two sides of the current collector, so that the electron transfer between the current collector and a battery case is greatly influenced, and the performance of the lithium ion battery is influenced. The nickel cobaltate is difficult to grow on one surface of the copper foil, even if the nickel cobaltate grows on one surface, the copper foil without the nickel cobaltate-loaded surface is directly oxidized to form copper oxide in the phase forming process of the nickel cobaltate at high temperature, and the electron transfer between a current collector and a battery shell is also influenced, so that the performance of the lithium ion battery is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a lithium ion battery cathode based on an in-situ grown copper oxide/nickel cobaltate nanowire composite material, the other surface of a copper foil is covered in a flexible and detachable manner, the copper foil without a nickel cobaltate-loaded surface is effectively prevented from being oxidized, and the trace copper oxide on the nickel cobaltate-loaded nanowire surface can not only contribute to partial specific capacity, but also has a synergistic effect with the nickel cobaltate nanowire, so that the performance of the lithium ion battery is greatly improved.
The technical scheme of the invention is as follows: a preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material comprises the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner liner of the hydrothermal reaction kettle, etching by hydrochloric acid solution to remove oxide components on the surface of the copper foil and simultaneously roughen the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by deionized water and ethanol, and then drying in vacuum at 60 ℃ for 8 hours;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off the outer ring of the white paper with the thickness of about 0.3 cm on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the white paper in the middle, so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowires on one side of a copper foil, wherein the molar ratio is 1: 2: 10-100: 1.5 dispersing the soluble nickel salt, the soluble cobalt salt, the urea and the hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5-2 h for later use, putting the copper foil covered in the step S2) into the lining of a hydrothermal kettle, pouring the standby solution with a copper foil adhesive tape facing downwards, reacting for 5-10 h at 100-180 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using the deionized water and ethanol respectively;
s4), drying the copper foil obtained in the step S3) for 8-24h at the temperature of 60 ℃, calcining the copper foil for 2-6 h in a muffle furnace at the temperature of 300 ℃, and raising the temperature at the speed of 1-3 ℃/min to obtain the copper oxide/nickel cobaltate nanowire composite material;
s5), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S4) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate;
s6), assembling the button cell, taking the negative plate of the copper oxide/nickel cobaltate nanowire composite lithium ion battery as a working electrode, taking a metal lithium plate as a reference electrode and a counter electrode, putting a diaphragm to separate the working electrode and the reference electrode, dropping electrolyte, pressing the battery more tightly by using a gasket and a spring plate, assembling to obtain the button cell, and carrying out electrochemical test on the assembled battery.
Further, in step S1), the thickness of the copper foil is 9 μ M, and the concentration of the etching hydrochloric acid is 2M.
Further, in step S2), the copper foil tape is a high temperature resistant tape.
Further, in step S3), the soluble nickel salt is Ni (NO)3)2·6H2O, nickel acetate and nickel chloride, and the soluble cobalt salt is Co (NO)3)2·6H2O, cobalt acetate and cobalt chloride.
Further, in step S5), the active material loading amount obtained is 0.8mg to 2.2 mg.
Further, in step S6), the electrolyte should completely infiltrate the inside of the battery, and the electrolyte used is 1M LiPF 6.
Further, in step S6), all the assembling is performed in a glove box with inert gas protection to obtain a button cell, the assembled cell needs to be left standing for 8-24h, a CR2030 type button cell is used as a test carrier, and the test voltage range is 0.01-3V.
The invention has the beneficial effects that:
1. according to the invention, one surface of the copper foil is flexibly and detachably covered, and the nickel cobaltate nanowire grows in situ on one surface of the copper foil, so that the problem of electronic conduction between the current collector and the battery shell is solved;
2. in the process of forming a phase of nickel cobaltate at high temperature, trace copper oxide can be formed, small part of specific capacity can be contributed, and the copper oxide/nickel cobaltate nanowire composite material lithium ion battery cathode performance can be improved together with the nickel cobaltate;
3. the battery provided by the invention has the capacity of 100mAg-1In the long-cycle test of current density, the high-capacity cycle can be realized, the stability is good, and the charging specific capacity to the 60 th circle is still 1309.07mAhg-1Compared with the prior art, the specific capacity and the rate capability of the in-situ growth nickel cobaltate lithium ion negative electrode material are further improved.
Drawings
FIG. 1 is an SEM image of a nickel cobaltate/carbon composite material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a nickel cobaltate/carbon composite material prepared in example 1 of the present invention;
fig. 3 is a constant current charge and discharge diagram of the battery prepared in example 1 of the present invention;
FIG. 4 is a graph of rate performance for a battery prepared in example 1 of the present invention;
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
A preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material comprises the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner lining of the hydrothermal reaction kettle, etching by using a hydrochloric acid solution with the concentration of 2M to remove oxide components on the surface of the copper foil, simultaneously roughening the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by using deionized water and ethanol, and then drying in vacuum for 8 hours at the temperature of 60 ℃;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off the outer ring of the white paper with the thickness of about 0.3 cm on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the white paper in the middle, so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowires on one side of a copper foil, and mixing 0.4362g of soluble nickel salt Ni (NO)3)2·6H2O, 0.8731g of Co (NO)3)2·6H2Dispersing 0.3242g of urea and 0.1418g of hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5h for later use, putting the copper foil covered in the step S2) into the lining of the hydrothermal kettle, pouring the standby solution with the copper foil adhesive tape facing downwards, reacting for 5h at 150 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using deionized water and ethanol respectively; drying for 12h at the temperature of 60 ℃, calcining for 3h by using a muffle furnace at the temperature of 300 ℃, and raising the temperature at the speed of 2 ℃/min to obtain the copper oxide/nickel cobaltate nanowire composite material, wherein the SEM image of the prepared copper oxide/nickel cobaltate nanowire composite material is shown in figure 1, and the XRD image is shown in figure 2;
s4), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S3) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate;
s5), assembling the button cell, taking a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate as a working electrode, taking a metal lithium plate as a reference electrode and a counter electrode, putting a diaphragm to separate the working electrode from the reference electrode, dropping 1M LiPF6 in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolyte, pressing the cell more tightly by using a gasket and a spring plate, taking a CR2030 type button cell as a test carrier, and performing all assembly in a glove box with inert gas protection to obtain the button cell;
s6), standing the assembled battery for 8h, and then carrying out electrochemical test to test the lithium ion battery with 100mAg-1The test voltage range is 0.01-3V, the constant-current charge-discharge cycle performance is shown in figure 3, and the multiplying power performance is shown in figure 4.
Example 2
A preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material comprises the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner lining of the hydrothermal reaction kettle, etching by using a hydrochloric acid solution with the concentration of 2M to remove oxide components on the surface of the copper foil, simultaneously roughening the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by using deionized water and ethanol, and then drying in vacuum for 8 hours at the temperature of 60 ℃;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off the outer ring of the white paper with the thickness of about 0.3 cm on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the white paper in the middle, so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowire on one side of copper foil, and adding 0.2908g of soluble nickel salt Ni (NO)3)2·6H2O, 0.5821g of Co (NO)3)2·6H2Dispersing 0.2161g of urea and 0.0945g of hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5h for later use, putting the copper foil covered in the step S2) into the inner liner of the hydrothermal kettle, pouring the standby solution with the copper foil adhesive tape facing downwards, reacting for 5h at 150 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using deionized water and ethanol respectively; drying for 12h at the temperature of 60 ℃, calcining for 3h in a muffle furnace at the temperature of 300 ℃, and raising the temperature at the speed of 2 ℃/min to obtain the copper oxide/nickel cobaltate nanowire composite material;
s4), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S3) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate;
s5), assembling the button cell, taking a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate as a working electrode, taking a metal lithium plate as a reference electrode and a counter electrode, putting a diaphragm to separate the working electrode from the reference electrode, dropping 1M LiPF6 in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolyte, pressing the cell more tightly by using a gasket and a spring plate, taking a CR2030 type button cell as a test carrier, and performing all assembly in a glove box with inert gas protection to obtain the button cell;
s6), standing the assembled battery for 8h, and then carrying out electrochemical test to test the lithium ion battery with 100mAg-1The long cycle performance of the test voltage range is 0.01-3V.
Example 3
A preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material comprises the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner lining of the hydrothermal reaction kettle, etching by using a hydrochloric acid solution with the concentration of 2M to remove oxide components on the surface of the copper foil, simultaneously roughening the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by using deionized water and ethanol, and then drying in vacuum for 8 hours at the temperature of 60 ℃;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off the outer ring of the white paper with the thickness of about 0.3 cm on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the white paper in the middle, so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowires on one side of a copper foil, and mixing 0.3635g of soluble nickel salt Ni (NO)3)2·6H2O, 0.7276g of Co (NO)3)2·6H2Dispersing 0.2702g of urea and 0.1182g of hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5h for later use, putting the copper foil covered in the step S2) into the lining of the hydrothermal kettle, pouring the standby solution with the copper foil adhesive tape facing downwards, reacting for 5h at 150 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using deionized water and ethanol respectively; drying for 12h at the temperature of 60 ℃, calcining for 3h in a muffle furnace at the temperature of 300 ℃, and raising the temperature at the speed of 2 ℃/min to obtain the copper oxide/nickel cobaltate nanowire composite material;
s4), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S3) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate;
s5), assembling the button cell, taking a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate as a working electrode, taking a metal lithium plate as a reference electrode and a counter electrode, putting a diaphragm to separate the working electrode from the reference electrode, dropping 1M LiPF6 in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolyte, pressing the cell more tightly by using a gasket and a spring plate, taking a CR2030 type button cell as a test carrier, and performing all assembly in a glove box with inert gas protection to obtain the button cell;
s6), standing the assembled battery for 8h, and then carrying out electrochemical test to test the lithium ion battery with 100mAg-1The long cycle performance of the test voltage range is 0.01-3V.
Example 4
A preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material comprises the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner lining of the hydrothermal reaction kettle, etching by using a hydrochloric acid solution with the concentration of 2M to remove oxide components on the surface of the copper foil, simultaneously roughening the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by using deionized water and ethanol, and then drying in vacuum for 8 hours at the temperature of 60 ℃;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off the outer ring of the white paper with the thickness of about 0.3 cm on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the white paper in the middle, so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowires on one side of a copper foil, and mixing 0.5816g of soluble nickel salt Ni (NO)3)2·6H2O, 1.1624g of Co (NO)3)2·6H2Dispersing 0.4322g of urea and 0.1418g of hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5h for later use, putting the copper foil covered in the step S2) into the lining of the hydrothermal kettle, pouring the standby solution with the copper foil adhesive tape facing downwards, reacting for 5h at 150 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using deionized water and ethanol respectively; drying at 60 deg.C for 12 hr, and dryingCalcining for 3 hours in a muffle furnace at the temperature of 300 ℃ at the heating speed of 2 ℃/min to obtain the copper oxide/nickel cobaltate nanowire composite material;
s4), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S3) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate;
s5), assembling the button cell, taking a copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate as a working electrode, taking a metal lithium plate as a reference electrode and a counter electrode, putting a diaphragm to separate the working electrode from the reference electrode, dropping 1M LiPF6 in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1:1 by volume) electrolyte, pressing the cell more tightly by using a gasket and a spring plate, taking a CR2030 type button cell as a test carrier, and performing all assembly in a glove box with inert gas protection to obtain the button cell;
s6), standing the assembled battery for 8h, and then carrying out electrochemical test to test the lithium ion battery with 100mAg-1The long cycle performance of the test voltage range is 0.01-3V.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (8)
1. A preparation method of a lithium ion battery cathode based on in-situ growth of a copper oxide/nickel cobaltate nanowire composite material is characterized by comprising the following steps:
s1), copper foil pretreatment, cutting the copper foil into a circle with the diameter equivalent to that of the inner lining of the hydrothermal reaction kettle, etching by hydrochloric acid solution to remove oxide components on the surface of the copper foil and simultaneously roughen the surface of the copper foil, cleaning the hydrochloric acid solution on the copper foil by deionized water and ethanol, and then drying for 8 hours in vacuum at the temperature of 60 ℃;
s2), covering one surface of the copper foil by using a copper foil adhesive tape, cutting the copper foil adhesive tape into the size same as that of the copper foil in the step S1), cutting off 0.3 cm of outer circle of white paper on the adhesive surface of the copper foil adhesive tape by using scissors, leaving the middle white paper so that the copper foil in the step S1) is not completely adhered to the copper foil adhesive tape, and wiping the copper foil clean by using ethanol;
s3), growing copper oxide/nickel cobaltate nanowires on one side of a copper foil, wherein the molar ratio is 1: 2: 10-100: 1.5 dispersing the soluble nickel salt, the soluble cobalt salt, the urea and the hexadecyl trimethyl ammonium bromide in deionized water, stirring for 0.5-2 h for later use, putting the copper foil covered in the step S2) into the lining of a hydrothermal kettle, pouring the standby solution with a copper foil adhesive tape facing downwards, reacting for 5-10 h at 100-180 ℃, taking out the copper foil after cooling to room temperature, and cleaning for 3 times by using the deionized water and ethanol respectively;
s4), drying the copper foil obtained in the step S3) for 8-24 hours at the temperature of 60 ℃, then transferring the copper foil to a muffle furnace, heating the muffle furnace to 300 ℃, continuously calcining for 2-6 hours at the heating speed of 1-3 ℃/min, and obtaining the copper oxide/nickel cobaltate nanowire composite material;
s5), preparing a negative plate of the lithium ion battery with the copper oxide/nickel cobaltate nanowire composite material, and shearing the part, adhered with the copper foil, of the copper foil adhesive tape by using scissors from the in-situ grown copper oxide/nickel cobaltate nanowire composite material plate obtained in the step S4) so as to obtain the nickel cobaltate nanowire copper foil with a long single surface; and (3) cutting the single-sided long nickel cobaltate nanowire copper foil into a wafer of 12mm to obtain the copper oxide/nickel cobaltate nanowire composite material lithium ion battery negative plate.
2. The method for preparing the lithium ion battery cathode based on the in-situ growth of the copper oxide/nickel cobaltate nanowire composite material according to claim 1 is characterized in that: in step S1), the thickness of the copper foil is 9 μ M, and the concentration of the etching hydrochloric acid is 2M.
3. The method for preparing the lithium ion battery cathode based on the in-situ growth of the copper oxide/nickel cobaltate nanowire composite material according to claim 1 is characterized in that: in the step S2), the copper foil adhesive tape is a high-temperature resistant adhesive tape.
4. The method for preparing the lithium ion battery cathode based on the in-situ growth of the copper oxide/nickel cobaltate nanowire composite material according to claim 1 is characterized in that: in step S3), the soluble nickel salt is Ni (NO)3)2·6H2One or more of O, nickel acetate and nickel chloride, and the soluble cobalt salt is Co (NO)3)2·6H2One or more of O, cobalt acetate and cobalt chloride.
5. The method for preparing the lithium ion battery cathode based on the in-situ growth of the copper oxide/nickel cobaltate nanowire composite material according to claim 1 is characterized in that: in step S5), the active substance loading obtained is 0.8mg to 2.2 mg.
6. A battery is characterized by comprising the lithium ion battery cathode prepared by the method of any one of claims 1 to 5, wherein the battery takes the copper oxide/nickel cobaltate nanowire composite lithium ion battery cathode sheet of any one of claims 1 to 5 as a working electrode, a metal lithium sheet as a reference electrode and a counter electrode, a diaphragm is arranged to separate the working electrode and the reference electrode, electrolyte is dripped, a gasket and a spring sheet are used for pressing the battery more tightly, a button battery is assembled, and the assembled battery is subjected to electrochemical test.
7. A battery according to claim 6, wherein: the electrolyte needs to completely infiltrate the inside of the whole battery, and the electrolyte used is 1M LiPF6。
8. A battery according to claim 6, wherein: all the assembling is carried out in a glove box with inert gas protection to obtain the button cell, the assembled cell needs to stand for 8-24 hours, the button cell is used as a test carrier, and the test voltage is 0.01-3V.
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