CN109244408B - Self-supporting double-carbon-layer composite-structure lithium ion battery cathode and preparation method thereof - Google Patents
Self-supporting double-carbon-layer composite-structure lithium ion battery cathode and preparation method thereof Download PDFInfo
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- CN109244408B CN109244408B CN201811095033.3A CN201811095033A CN109244408B CN 109244408 B CN109244408 B CN 109244408B CN 201811095033 A CN201811095033 A CN 201811095033A CN 109244408 B CN109244408 B CN 109244408B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 44
- 239000004917 carbon fiber Substances 0.000 claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004744 fabric Substances 0.000 claims abstract description 27
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 22
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 229940044658 gallium nitrate Drugs 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000009423 ventilation Methods 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002355 dual-layer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention provides a self-supporting double-carbon-layer composite-structure lithium ion battery cathode and a preparation method thereof. The method comprises the following steps: weighing polyvinyl butyral, dissolving the polyvinyl butyral in ethanol, stirring to obtain a colloidal solution, adding gallium nitrate and glucose, and stirring to form a uniform colloidal solution; dropwise adding the colloidal solution on the surface of the hydrophilic carbon fiber fabric until the surface is completely soaked, and placing the fabric at room temperature for ventilation drying; continuously drying the obtained product in an oven, and sintering the dried product in a tubular furnace at 400-650 ℃ under the condition of nitrogen or argon to obtain carbon-coated Ga2O3And coating the carbon fiber composite material. The material takes carbon fiber as a template, and utilizes high polymer molecules with viscosity, glucose and Ga2O3Uniformly compounding and reinforcing Ga2O3Contacting with a carbon substrate to form a self-supporting carbon-carbon dual-layer coatingGa2O3The carbon fiber composite structure is coated and directly used as the cathode of the lithium ion battery. Resulting carbon-coated Ga2O3The coated carbon fiber composite material can be used for a lithium ion battery cathode, can show good electrochemical performance characteristics, and has good application prospects.
Description
Technical Field
The invention relates to a lithium ion battery cathode, in particular to a self-supporting double carbon layer carbon-coated Ga2O3And a preparation method of a coated carbon fiber composite structure, belonging to the field of electrochemical power sources.
Technical Field
The environmental pollution problem caused by the large consumption of the traditional fossil energy sources brings certain impact on the rapid development of social economy. The rapid development of new energy industry reflects the gradually enhanced consciousness of human society for improving the existing unreasonable energy structure. People can effectively utilize novel clean energy and renewable clean energy with the characteristics of randomness, intermittence and the like on the earth by researching high-performance conversion devices and energy storage equipment. The lithium ion battery is widely applied to the field of electrochemical energy storage by virtue of the advantages of cleanness, high efficiency, light weight, long cycle life and the like.
In recent years, with the rise of new hybrid electric vehicles and pure electric vehicles, the research and development of high-energy-density and high-power-density lithium ion batteries are urgent, and the development of new high-performance electrode materials is urgently needed. The transition metal compound has high theoretical capacity characteristic and is a research hotspot of novel cathode materials.
Gallium-based compounds have a wide range of applications. For example, gallium oxide thin film semiconductor materials have unique optical and electrical properties and are widely used in power devices. Recently, Ga2O3And the GaN is used as the lithium ion battery cathode material, shows higher theoretical capacity and has potential application value. However, Ga2O3The lithium ion battery cathode material has the problems of poor conductivity (close to an insulator), large volume effect and the like, so that the electrochemical performance of the lithium ion battery cathode material is not ideal. Conventional approaches to improving the electrochemical performance of the conversion-type electrode material include carbon recombination and conductive self-supporting structural design. At present, Ga is concerned2O3Research on the design of self-supporting electrodes has not been reported.
Disclosure of Invention
Based on the background, the invention discloses a carbon-coated Ga2O3The carbon fiber-coated self-supporting electrode structure comprises a carbon fiber layer and Ga from inside to outside in sequence2O3A layer, a carbon layer; in the process, the carbon-coated Ga is formed firstly2O3Then coating the carbon with Ga2O3The coated carbon fiber is used as a negative electrode of a lithium ion battery and shows excellent electrochemical performance.
The invention combines sol deposition and high-temperature sintering to prepare carbon-coated Ga2O3And coating the carbon fiber self-supporting electrode. Firstly, proper gallium nitrate and glucose are dissolved in polyvinyl butyral colloidal solution, then hydrophilic carbon fiber fabrics are soaked in the obtained solution, and then the fabrics are taken out and dried. Finally, obtaining the carbon-coated Ga by high-temperature sintering2O3And (3) coating the carbon fiber composite structure. The double carbon structure can greatly improve Ga2O3And volume effects during cycling, thereby enhancing its performance.
The invention relates to a preparation method of a self-supporting electrode of a lithium ion battery, wherein the electrode structure is carbon-coated Ga2O3And coating the carbon fibers. Prepared self-supporting double carbon-coated Ga2O3The coated carbon fiber composite structure can be used as a lithium ion battery cathode and shows good electrochemical performance.
Carbon-coated Ga2O3The specific preparation method of the coated carbon fiber negative electrode material comprises the following steps:
(1) weighing polyvinyl butyral, dissolving in ethanol, stirring at a constant temperature of 50-70 ℃ until a uniform colloidal solution is formed, and cooling to room temperature;
(2) weighing gallium nitrate and glucose powder, dissolving in the colloidal solution, and stirring to form uniform colloidal solution;
(3) dropwise adding the colloidal solution on the surface of the hydrophilic carbon fiber fabric until the surface is completely soaked, and placing the fabric at room temperature for ventilation drying;
(4) nature of natureDrying at 60-80 ℃ for 3-6h, sintering at 400-650 ℃ in a tubular furnace under the condition of nitrogen or argon for 3-12 h to obtain carbon-coated Ga2O3And coating the carbon fiber composite material.
The molecular weight of the polyvinyl butyral is = 90000-120000.
The unit volume mass of the prepared polyvinyl butyral colloidal solution is 0.01-0.2 g/ml; the molar ratio of the polyvinyl butyral to the gallium nitrate to the glucose is 0.001-0.02: 2-10: 1. The carbon-coated Ga2O3And coating Ga in the carbon fiber composite material2O3The total mass ratio of the carbon to the carbon is 1-5: 1; the carbon comprises the total mass of the coated carbon and the carbon fiber. The sintering temperature is 400-550 ℃.
The hydrophilic carbon fiber fabric comprises various commercial carbon cloth subjected to hydrophilic treatment by physical and chemical methods, carbon fibers prepared by an electrospinning technology and the like, and the size of the hydrophilic carbon fiber fabric is 3cm by 4 cm.
The principle of this patent lies in: before the polyvinyl butyral colloidal solution is utilized to fully disperse the gallium nitrate and the glucose
And driving the body, and forming effective combination with the precursor. The polyvinyl butyral colloidal solution has strong binding force with a carbon substrate, and can be used as a binding reinforcing phase of a carbon fiber fabric and a precursor solution. Meanwhile, in the sintering process, when gallium oxide is formed, the polyvinyl butyral carbonizes with the glucose site, and the formed carbon can effectively inhibit the growth of gallium oxide particles and remarkably enhance the contact with a substrate, so that the high reaction activity and the high conductivity of the electrode are ensured.
The self-supporting dual carbon layer carbon coated Ga to which this patent relates2O3The lithium ion battery cathode with the coated carbon fiber composite structure and the preparation method thereof have the following characteristics:
(1) the electrode preparation method is simple and controllable, and has good repeatability;
(2) sintered carbon-coated Ga2O3The coated carbon fiber composite structure can be directly used as a lithium ion battery cathode without an additional electrode preparation process;
(3) colloidal solution of glucose and polyvinyl butyralThe liquid can obviously reinforce the carbon fiber fabric substrate and Ga2O3In the form of a bond between them.
(4) The double-carbon composite structure synthesized by the method can effectively improve the conductivity of the electrode material in the circulation process and effectively improve Ga2O3The semiconductor material has the cycling stability in the lithium ion battery, and can effectively relieve Ga2O3Volume changes during cycling, maintaining electrode integrity.
Drawings
Figure 1 XRD pattern of the sample prepared in example 1.
FIG. 2 SEM image of sample prepared in example 1.
Fig. 3 graph of the first three charge and discharge curves and cycle performance of the sample prepared in example 1.
FIG. 4 is a graph of the cycle performance of the samples prepared in example 2.
FIG. 5 cycle performance plot of the samples prepared in example 3.
Detailed Description
Example 1
Weighing 0.5g of polyvinyl butyral (PVB, molecular weight = 90000-120000) and dissolving in 10ml of ethanol, stirring at a constant temperature of 60 ℃ until a uniform colloidal solution is formed, and cooling to room temperature; weighing 1.024g of gallium nitrate and 0.4g of glucose powder, dissolving in the colloidal solution, and stirring to form a uniform colloidal solution; selecting a piece of treated hydrophilic carbon fiber fabric with the size of 3cm by 4cm, dripping colloidal solution on the surface of the fabric until the fabric is completely soaked, and placing the fabric at room temperature for ventilation and drying; the obtained product is dried continuously in a 70 ℃ oven for 5h and then sintered in a 550 ℃ tube furnace for 5h under the condition of air or nitrogen to obtain carbon-coated Ga2O3And coating the carbon fiber composite material. The prepared sample is analyzed by XRD pattern, as shown in figure 1, all diffraction peaks and Ga2O3(XRD card JCPDS, NO. 87-1901) shows that carbon-coated Ga is successfully prepared2O3And coating the carbon fiber composite material. SEM representation is carried out on the sample, and as can be seen from figure 2, the surfaces of the single carbon fibers of the hydrophilic carbon fiber fabric are coated with uniform carbon coatingsGa-coated2O3And (3) a layer. Coating the carbon obtained in the step with Ga2O3The coated carbon fiber composite material is cut into small pieces of 0.5cm by 0.5cm, and vacuum-dried at 120 ℃ for 12 h. The method is characterized in that a metal lithium sheet is used as a counter electrode, a Celgard membrane is used as a diaphragm, and the electrolyte is a universal lithium ion battery electrolyte 1M LiPF6EC =1: 1, assembled into CR2025 type cells in an argon-protected glove box. And standing for 8 hours after the battery is assembled, and then performing constant-current charging and discharging tests by using a CT2001A battery test system, wherein the test voltage is 0.02-2V. FIG. 3 shows carbon-coated Ga prepared in example 12O3The coated carbon fiber electrode has the first charge and discharge specific capacities of 732.3 mAh/g and 1009.7 mAh/g under the current density of 0.15A/g, and embodies better electrochemical performance characteristics.
Example 2
Weighing 0.5g of polyvinyl butyral (PVB, MW = 90000-120000) and dissolving in 10ml of ethanol, stirring at the constant temperature of 60 ℃ until a uniform colloidal solution is formed, and cooling to room temperature; weighing 1.024g of gallium nitrate and 0.4g of glucose powder, dissolving in the colloidal solution, and stirring to form a uniform colloidal solution; selecting a piece of treated hydrophilic carbon fiber fabric with the size of 3cm by 4cm, dripping colloidal solution on the surface of the fabric until the fabric is completely soaked, and placing the fabric at room temperature for ventilation and drying; the obtained product is dried continuously in a 70 ℃ oven for 5h and then sintered in a 450 ℃ tube furnace for 5h under the condition of air or nitrogen to obtain carbon-coated Ga2O3And coating the carbon fiber composite material. The cell was assembled in the manner of example 1. FIG. 4 shows carbon-coated Ga prepared in example 22O3The first charge and discharge specific capacity of the coated carbon fiber electrode under the current density of 0.15A/g is 679mAh/g and 999.1 mAh/g.
Example 3
Weighing 0.5g of polyvinyl butyral (PVB, MW = 90000-120000) and dissolving in 10ml of ethanol, stirring at the constant temperature of 60 ℃ until a uniform colloidal solution is formed, and cooling to room temperature; weighing 1.024g of gallium nitrate and 0.4g of glucose powder, dissolving in the colloidal solution, and stirring to form a uniform colloidal solution; selecting a piece of treated hydrophilic carbon with the size of 3cm to 4cmDripping colloidal solution on the surface of the fiber fabric until the fiber fabric is completely soaked, and placing the fiber fabric at room temperature for ventilation drying; the obtained product is dried continuously in a 70 ℃ oven for 5h and then sintered in a 650 ℃ tube furnace for 5h under the condition of air or nitrogen to obtain carbon-coated Ga2O3And coating the carbon fiber composite material. The cell was assembled in the manner of example 1. FIG. 5 shows carbon-coated Ga prepared in example 32O3The first charge and discharge specific capacity of the coated carbon fiber electrode under the current density of 0.15A/g is 690.5 mAh/g and 1004.3 mAh/g.
Claims (5)
1. A preparation method of a self-supporting double-carbon-layer lithium ion battery cathode material is characterized by comprising the following specific preparation processes:
(1) weighing polyvinyl butyral, dissolving the polyvinyl butyral in ethanol, stirring the polyvinyl butyral at the constant temperature of 50-70 ℃ until a uniform colloidal solution is formed, and cooling the solution to room temperature, wherein the molecular weight of the polyvinyl butyral is 90000-120000;
(2) weighing gallium nitrate and glucose powder, dissolving in the colloidal solution, and stirring to form uniform colloidal solution;
(3) dropwise adding the colloidal solution on the surface of the hydrophilic carbon fiber fabric until the surface is completely soaked, and placing the fabric at room temperature for ventilation drying;
(4) after natural drying, continuously drying at 60-80 ℃ for 3-6h, and sintering in a tubular furnace at 400-650 ℃ under the condition of nitrogen or argon for 3-12 h to obtain carbon-coated Ga2O3And is coated with a carbon fiber composite material.
2. The method of claim 1, wherein: the hydrophilic carbon fiber fabric comprises hydrophilic carbon cloth and nano carbon fibers prepared by an electrospinning technology.
3. The method of claim 1, wherein: the unit volume mass of the prepared polyvinyl butyral colloidal solution is 0.01-0.2 g/ml; the molar ratio of the polyvinyl butyral to the gallium nitrate to the glucose is 0.001-0.02: 2-10: 1.
4. The method of claim 1, wherein: the sintering temperature in the step (4) is 400-550 ℃.
5. The method of claim 1, wherein: the carbon-coated Ga2O3And coating Ga in the carbon fiber composite material2O3The total mass ratio of the carbon to the carbon is 1-5: 1; the carbon comprises coated carbon and carbon fiber.
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| CN107732221A (en) * | 2017-11-27 | 2018-02-23 | 三峡大学 | A kind of stable compound lithium ion battery negative material α Ga2O3 and preparation method |
| CN108258225A (en) * | 2018-01-23 | 2018-07-06 | 福州大学 | A kind of preparation method of the three-dimensional porous array combination electrode material of nanocarbon/metal sulfide/carbon for lithium ion battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732221A (en) * | 2017-11-27 | 2018-02-23 | 三峡大学 | A kind of stable compound lithium ion battery negative material α Ga2O3 and preparation method |
| CN108258225A (en) * | 2018-01-23 | 2018-07-06 | 福州大学 | A kind of preparation method of the three-dimensional porous array combination electrode material of nanocarbon/metal sulfide/carbon for lithium ion battery |
Non-Patent Citations (5)
| Title |
|---|
| Achieving high mass loading of Na3V2(PO4)3@carbon on carbon cloth by constructing three-dimensional network between carbon fibers for ultralong cycle-life and ultrahigh rate sodium-ion batteries;Donglei Guo et al.;《Nano Energy》;20171227;第45卷;第136-147页 * |
| Aluminum oxideramorphous carbon coatings on carbon fibers,prepared by pyrolysis of an organic–inorganic hybrid precursor;P. Peng et al.;《Materials Letters》;20010131;第47卷;第171-177页 * |
| Fe2O3/碳布三维网络复合材料的制备与修饰及其储能应用;王小华;《中国优秀硕士学位论文全文数据库》;20180615(第06期);第23-40页 * |
| Graphene-Oxide-Assisted Synthesis of Ga2O3 Nanosheets/Reduced Graphene Oxide Nanocomposites Anodes for Advanced Alkali-Ion Batteries;Mingzhi Yang et al.;《ACS Appl. Energy Mater》;20180808;第1卷;第4708-4715页 * |
| High-Performance Ga2O3 Anode for Lithium-Ion Batteries;Xun Tang et al.;《ACS Appl. Mater. Interfaces》;20180118;第10卷;第5519-5526页 * |
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