CN106847520B - Lithium ion capacitor anode and application thereof - Google Patents
Lithium ion capacitor anode and application thereof Download PDFInfo
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- CN106847520B CN106847520B CN201611198215.4A CN201611198215A CN106847520B CN 106847520 B CN106847520 B CN 106847520B CN 201611198215 A CN201611198215 A CN 201611198215A CN 106847520 B CN106847520 B CN 106847520B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011267 electrode slurry Substances 0.000 claims abstract description 22
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002612 dispersion medium Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- 229910010736 Li5ReO6 Inorganic materials 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 229910008714 Li2NiO3 Inorganic materials 0.000 claims description 3
- 229910010648 Li6CoO4 Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims description 2
- 239000002003 electrode paste Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011888 foil Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910010177 Li2MoO3 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- -1 LiPF6 Chemical class 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a lithium ion capacitor anode and application thereof. The positive electrode comprises a current collector and a positive electrode material formed on the surface of the current collector, and the positive electrode material is a substance left after drying the positive electrode slurry; the positive electrode slurry is a solution formed by dissolving a positive electrode active substance, lithium metal oxide, conductive carbon black and a binder in a dispersion medium; the mass ratio of the positive electrode active material, the lithium metal oxide, the conductive carbon black and the binder is (70-85): 5-10): 3-10; the mass ratio of the total mass of the positive electrode active material, the lithium metal oxide, the conductive carbon black and the binder to the dispersion medium is 1: (5-7). The preparation of the anode of the lithium ion capacitor is realized through the lithium metal oxide, when the lithium ion capacitor is applied to the lithium ion capacitor, the lithium ion capacitor is charged to 4.2-5.0V under the condition of 0.02-0.1C and the voltage is stabilized for one time, and the formation process steps consuming time and consuming energy are simplified.
Description
Technical Field
The invention relates to a capacitor anode, in particular to a lithium ion capacitor anode and application thereof, belonging to the technical field of energy storage devices.
Background
Along with the acceleration of the novel urbanization process of 'green', 'intelligent', the development of novel green, high-efficient energy storage device is for the research focus. Among numerous novel energy storage devices, a lithium ion capacitor is used as a novel hybrid capacitor with the power characteristics of an electric double layer capacitor and the energy characteristics of a lithium ion battery, and becomes a novel breakthrough for improving the energy density of a super capacitor and the power density of a lithium ion battery system.
Generally, a lithium ion capacitor is composed of an adsorption and desorption energy storage activated carbon as a positive electrode, a reversible redox carbon material (such as graphite, hard carbon, soft carbon, etc.) as a negative electrode, and an organic electrolyte. Through the series connection process between the internal positive electrode and the internal negative electrode, the energy density of the traditional double-electric-layer capacitor is improved by more than 3 times, and the power density of the lithium ion battery is increased by more than 2 times, so that the energy storage power supply becomes an efficient energy storage power supply urgently needed in the application fields of urban public transport, wind power generation, heavy machinery and the like.
However, in the practical operation of the lithium ion capacitor, the formation of the interfacial film of the solid electrolyte on the surface of the negative electrode needs to be completed, so that the lithium pre-insertion process of the negative electrode becomes an essential process step. The Chinese invention patent (publication number: CN102969162A) discloses a positive plate of a lithium ion capacitor and a preparation method thereof, wherein the positive plate of the capacitor is not specially treated generally, namely, active carbon is used as the only energy storage material. For another example, chinese patent publication No. CN101138058A discloses a lithium ion capacitor, which mainly performs a "pre-lithium intercalation" process by establishing a "potential difference" between a negative electrode and a metal lithium source. Although the two methods can prepare the high specific energy lithium ion capacitor, lithium metal, namely high-activity metal, is required in the preparation process of the product, so that the production process has strict requirements on the working environment, safety level setting and batch production cost, and finally the large-scale application of the series of products is limited.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a lithium ion capacitor anode, which can avoid the problems of low safety coefficient, high production cost, long operation process and the like of a lithium ion capacitor and realize the processes of simple process and mass production amplification.
The purpose of the invention can be realized by the following technical scheme: the positive electrode of the lithium ion capacitor comprises a current collector and a positive electrode material formed on the surface of the current collector, wherein the positive electrode material is a substance left after drying positive electrode slurry;
the positive electrode slurry is a solution formed by dissolving a positive electrode active substance, lithium metal oxide, conductive carbon black and a binder in a dispersion medium;
the mass ratio of the positive active material to the lithium metal oxide to the conductive carbon black to the binder is (70-85) to (5-10) to (3-10);
the mass ratio of the total mass of the positive electrode active material, the lithium metal oxide, the conductive carbon black and the binder to the dispersion medium is 1: (5-7).
In the lithium ion capacitor anode, the anode slurry is prepared under the conditions of temperature of 22-28 ℃ and humidity of 20-40%.
In the lithium ion capacitor positive electrode, the solid content of the positive electrode slurry is 40-55%.
In the lithium ion capacitor anode, the anode active substance is activated carbon, and the specific surface area of the activated carbon is 1550-2100 m2(iv)/g, the surface acidic functional group content is less than 0.5meq/g, the ash content is less than 1%, and the metal impurity content is less than 100 ppm. The precursors of the raw materials used by the active carbon are petroleum coke, needle coke, coconut shells and the like.
In the above lithium ion capacitor positive electrode, the lithium metal oxide is Li6CoO4、Li6MnO4、Li5ReO6、Li2NiO3、Li2MoO3Of greater than 99.5% purity.
In the above lithium ion capacitor positive electrode, the binder is polyvinylidene fluoride, and the purity of the binder is greater than 99.5%.
Preferably, the current collector is a corrosion aluminum foil, a stainless steel foil or a mesh material, and the corrosion aluminum foil is non-porous or porous.
Another object of the present invention is to provide a lithium ion capacitor using the above positive electrode of the lithium ion capacitor,
the negative electrode of the lithium ion capacitor comprises a current collector and a negative electrode material formed on the surface of the current collector, wherein the negative electrode material is a substance left after drying the negative electrode slurry;
the negative electrode slurry is a solution formed by dissolving a negative electrode active material, conductive carbon black, a binder and a dispersing agent in a dispersing medium, wherein the mass ratio of the negative electrode active material to the conductive carbon black to the binder to the dispersing agent is (88-92) to (3-7) to (1-3).
In the lithium ion capacitor, the negative active material is a graphite carbon material, and comprises one or more of soft carbon, natural graphite, artificial graphite and hard carbon, and the purity of the negative active material is more than 99.5%.
Preferably, the current collector is an etched copper foil, a stainless steel foil or a mesh material, and the etched copper foil is non-porous or porous.
In the above lithium ion capacitor, the preparation method of the lithium ion capacitor includes: preparing positive and negative pole pieces, assembling a lithium ion capacitor and pre-embedding lithium;
the pre-lithium intercalation process comprises the following steps: and charging the assembled lithium ion capacitor to 4.3-5.0V under the condition of 0.02-0.1C, and keeping the voltage constant for 6-10h under the voltage condition.
Preferably, the assembling of the lithium ion capacitor comprises the steps of laminating the positive electrode, the diaphragm, the negative electrode and the diaphragm according to a Z shape to form a battery cell, placing the battery cell in an aluminum plastic film shell with a certain shell size, injecting electrolyte, and carrying out vacuum sealing to obtain the novel lithium ion capacitor.
Preferably, the electrolyte salt in the electrolyte is an organic solvent-soluble lithium salt, including LiPF6、LiBF4、LiClO4The organic solvent is at least one of PC, EC, DEC, DMC and EMC.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the preparation of the anode of the lithium ion capacitor is realized through the lithium metal oxide which has high capacity and is easy to generate the irreversible lithium removal process of lithium ions, the successful insertion of the lithium ions is finally completed, and active metal lithium is not required to be introduced in the lithium insertion process, so that the potential safety hazard caused by lithium metal exposure is avoided, and the process is safe and reliable.
2. In the preparation process of the lithium ion capacitor anode, the lithium metal oxide is added into the anode slurry in proportion in the slurry mixing process, no additional process condition and working environment requirement are needed, the production cost is low, and the operation is simple.
3. The method does not need a slow pre-lithium embedding process in the conventional lithium ion capacitor preparation process, and only needs to charge to 4.2-5.0V under the condition of 0.02-0.1C and stabilize the voltage once, so that the time-consuming and energy-consuming formation process steps are simplified.
Drawings
Fig. 1 shows the capacity retention rate of the lithium ion capacitor according to the present invention measured during long-term cyclic charge and discharge under 1C conditions.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1:
the specific surface area is 1550m2Active carbon with surface acid functional group content of 0.45meq/g, ash content of 0.8 percent and metal impurity content of 85ppm and Li with purity of more than 99.5 percent6CoO4The conductive carbon black and 10% polyvinylidene fluoride with the purity of more than 99.5% are weighed according to the mass ratio of 80:10:5:5, NMP with the mass ratio of 1:5 to the total mass of the positive electrode active substance, the lithium metal oxide, the conductive carbon black and the binder is dripped, and the positive electrode slurry with the solid content of 50% is prepared under the conditions of constant temperature of 25 ℃ and constant humidity of 30%. And uniformly coating the positive electrode slurry on the front surface and the back surface of a non-porous corrosion aluminum foil, and drying, rolling and punching to obtain the 55mm 75mm lithium ion capacitor positive electrode.
Example 2:
the specific surface area is 1700m2Active carbon with surface acid functional group content of 0.4meq/g, ash content of 0.9%, metal impurity content of 95ppm, and Li with purity of more than 99.5%6MnO4The conductive carbon black and 10% polyvinylidene fluoride with the purity of more than 99.5% are weighed according to the mass ratio of 85:6:5:4, NMP with the mass ratio of 1:5 to the total mass of the positive electrode active substance, the lithium metal oxide, the conductive carbon black and the binder is dripped, and the positive electrode slurry with the solid content of 50% is prepared under the conditions of constant temperature of 25 ℃ and constant humidity of 30%. And then uniformly coating the positive electrode slurry on the front surface and the back surface of the porous corrosion aluminum foil, and drying, rolling and punching to obtain the 55mm 75mm lithium ion capacitor positive electrode.
Example 3:
the specific surface area is 1850m2Active carbon with surface acid functional group content of 0.35meq/g, ash content of 0.75 percent and metal impurity content of 90ppm and Li with purity of more than 99.5 percent2NiO3Weighing conductive carbon black and 10% polyvinylidene fluoride with purity of more than 99.5% according to the mass ratio of 80:10:5:5, and dropwise adding the polyvinylidene fluoride and the positive electrode active materialNMP with the mass ratio of the total mass of the substances, the lithium metal oxide, the conductive carbon black and the binder being 1:5 is used for preparing the anode slurry with the solid content of 50% under the conditions of constant temperature of 25 ℃ and constant humidity of 30%. And then, uniformly coating the positive electrode slurry on the front surface and the back surface of the non-porous corrosion aluminum foil, and drying, rolling and punching to obtain the 55 mm-75 mm lithium ion capacitor positive electrode.
Example 4:
the specific surface area is 2100m2Active carbon with 0.48meq/g of surface acid functional group content, 0.7% of ash content and 60ppm of metal impurity content and Li with purity more than 99.5%2MoO3The conductive carbon black and 10% polyvinylidene fluoride with the purity of more than 99.5% are weighed according to the mass ratio of 84:5:5:6, NMP with the mass ratio of 1:5 to the total mass of the positive electrode active substance, the lithium metal oxide, the conductive carbon black and the binder is dripped, and the positive electrode slurry with the solid content of 50% is prepared under the conditions of constant temperature of 25 ℃ and constant humidity of 30%. And then, uniformly coating the positive electrode slurry on the front surface and the back surface of the non-porous corrosion aluminum foil, and drying, rolling and punching to obtain the 55 mm-75 mm lithium ion capacitor positive electrode.
Application examples 1 to 4:
the lithium ion capacitor positive electrodes prepared in the above examples 1 to 4 were applied to a lithium ion capacitor.
The negative electrode of the lithium ion capacitor is: the preparation method comprises the steps of weighing soft carbon with the purity of more than 99.5%, conductive carbon black, 40% styrene butadiene rubber and 1.5% of sodium hydroxymethyl cellulose according to the mass ratio of 91:5:2:2, and dropwise adding deionized water with the mass ratio of 1:4.2 to active substances, and stirring for 2 hours under a vacuum condition to prepare the cathode slurry. And then uniformly coating the negative electrode slurry on the front surface and the back surface of the non-porous corrosion copper foil, and drying, rolling and punching to obtain the negative electrode with the thickness of 55mm x 75 mm.
Laminating the positive electrode, the diaphragm, the negative electrode and the diaphragm in a Z-shaped mode, placing the laminated positive electrode, the diaphragm, the negative electrode and the diaphragm into an aluminum-plastic film shell of an outer shell, and injecting 1M LiPF6(the solvent is EC and DMC with the volume ratio of 1: 1) electrolyte, and the lithium ion capacitor can be obtained after vacuum pumping and sealing.
And then charging the monomer to 4.5V by the lithium ion capacitor at the current of 0.06C, and stabilizing the voltage for 10h to obtain the lithium ion capacitor completing the pre-lithium embedding process.
The lithium ion capacitors prepared in application examples 1 to 4 were subjected to a long-term cyclic charge and discharge process under a condition of 1C to test the capacity retention rate, and the test results are shown in fig. 1. As can be seen from fig. 1: after 1000 cycles, the capacity retention rate is more than 92%.
In the above embodiments and alternatives, the mass ratio of the positive electrode active material, the lithium metal oxide, the conductive carbon black, and the binder may also be 70:10:10:10, 72:9: 10, 72:10:9:9, 75:10:7:8, 75:8:7:10, 78:8:7:7, 80:8:3:9, 80:9:4:7, 81:9:7:3, 82:8:5:5, 82:6:6:6, 83:7:5:5, 83:5:8: 4.
In the above-described embodiment and its alternatives, the mass ratio of the total mass of the cathode active material, the lithium metal oxide, the conductive carbon black, and the binder to the dispersion medium NMP may also be 1: 5.1, 1: 5.2, 1: 5.3, 1: 5.4, 1: 5.5, 1: 5.6, 1: 5.7, 1: 5.8, 1: 5.9, 1: 6.0, 1: 6.1, 1: 6.2, 1: 6.3, 1: 6.4, 1: 6.5, 1: 6.6, 1: 6.7, 1: 6.8, 1: 6.9, 1: 7.0.
in the embodiment and the alternative scheme, the specific surface area of the activated carbon can be 1550-2100 m2Between/g, e.g. 1580m2/g、1600m2/g、1650m2/g、1750m2/g、1900m2/g、1950m2/g、1980m2/g、2000m2/g、2050m2An arbitrary value such as,/g, an arbitrary value such as 0.1meq/g, 0.15meq/g, 0.2meq/g, 0.25meq/g, 0.3meq/g, etc., having a surface acidic functional group content of less than 0.5meq/g, an arbitrary value such as 0.3%, 0.4%, 0.5%, 0.6%, 0.85%, 0.95%, etc., having an ash content of less than 1%, an arbitrary value such as 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 70ppm, etc., having a metal impurity content of less than 100 ppm.
In the above embodiments and alternatives, the temperature during the preparation of the positive electrode slurry may also be 22 ℃, 23 ℃, 24 ℃, 26 ℃, 27 ℃, 28 ℃.
In the above embodiment and its alternatives, the humidity during the preparation of the positive electrode slurry may also be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%.
In the above examples and alternatives thereof, the solid content of the cathode slurry may also be 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 51%, 52%, 53%, 54%, 55%.
In the above embodiments and alternatives, the lithium metal oxide may also be Li5ReO6Or Li6CoO4、Li6MnO4、Li2NiO3、Li5ReO6、Li2MoO3Any two, three, four, and five of them.
In the application example and the alternative, the mass ratio of the negative electrode active material, the conductive carbon black, the binder, and the dispersant may be 90:5:3:2, 92:4:2:2, 89:7:3:1, 88:7:2:3, 92:3:3:2, 91:4:3:2, 90:6:2:2, 90:4:3:3, and 91:6:1: 2.
In the above application examples and their alternatives, the negative active material may also be natural graphite, artificial graphite, hard carbon, or a mixture of any two, three, or four of soft carbon, natural graphite, artificial graphite, and hard carbon.
In the application example and the alternative scheme thereof, the mass ratio of the total mass of the negative electrode active material, the conductive carbon black, the binder and the dispersant to the deionized water as the dispersion medium may be 1:4, 1: 4.1, 1: 4.3, 1: 4.4, 1: 4.5, 1: 4.6, 1: 4.7, 1: 4.8, 1: 4.9, 1: 5.0.
in the above application examples and their alternatives, the charging conditions of the lithium ion capacitor during the pre-lithium intercalation process may also be 0.02C, 0.03C, 0.04C, 0.05C, 0.07C, 0.08C, 0.09C, 0.1C, 4.3V, 4.4V, 4.6V, 4.7V, 4.8V, 4.9V, 5.0V, constant voltage 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5 h.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. Therefore, the contents of the verification of each example are not described one by one here, and only examples 1 to 4 and application examples 1 to 4 are used as representatives to describe the excellent points of the present invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (5)
1. The lithium ion capacitor is characterized in that a negative electrode of the lithium ion capacitor comprises a current collector and a negative electrode material formed on the surface of the current collector, wherein the negative electrode material is a substance left after drying a negative electrode slurry;
the negative electrode slurry is a solution formed by dissolving a negative electrode active substance, conductive carbon black, a binder and a dispersing agent in a dispersing medium, wherein the mass ratio of the negative electrode active substance to the conductive carbon black to the binder to the dispersing agent is (88-92) to (3-7) to (1-3);
the positive electrode comprises a current collector and a positive electrode material formed on the surface of the current collector, wherein the positive electrode material is a substance left after drying the positive electrode slurry;
the positive electrode slurry is a solution formed by dissolving a positive electrode active substance, lithium metal oxide, conductive carbon black and a binder in a dispersion medium;
the mass ratio of the positive active material to the lithium metal oxide to the conductive carbon black to the binder is (70-85) to (5-10) to (3-10);
the mass ratio of the total mass of the positive electrode active material, the lithium metal oxide, the conductive carbon black and the binder to the dispersion medium is 1 (5-7);
the positive active substance is active carbon, and the ratio table of the active carbonThe area is 1550 ~ 2100m and 2100m2(iv)/g, surface acidic functional group content is less than 0.5meq/g, ash content is less than 1%, metal impurity content is less than 100 ppm;
the lithium metal oxide is Li6CoO4、Li6MnO4、Li2NiO3、Li5ReO6Of greater than 99.5% purity;
the preparation method of the lithium ion capacitor comprises the following steps: preparing positive and negative pole pieces, assembling a lithium ion capacitor and pre-embedding lithium;
the pre-lithium embedding process comprises the steps of charging the assembled lithium ion capacitor to 4.3 ~ 5.0.0V under the condition of 0.02 ~ 0.1.1C, and keeping the voltage constant for 6-10h under the condition of voltage.
2. The lithium ion capacitor according to claim 1, wherein the positive electrode paste is prepared at a temperature of 22-28 ℃ and a humidity of 20-40%.
3. The lithium ion capacitor according to claim 1, wherein the solid content of the positive electrode slurry is 40-55%.
4. The lithium ion capacitor according to claim 1, wherein the binder is polyvinylidene fluoride, and the purity of the binder is greater than 99.5%.
5. The lithium ion capacitor according to claim 1, wherein the negative active material is a graphite-based carbon material comprising one or more of soft carbon, natural graphite and artificial graphite, and the purity of the carbon material is greater than 99.5%.
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| CN107680818A (en) * | 2017-08-15 | 2018-02-09 | 宁波中车新能源科技有限公司 | A kind of high rich lithium ion capacitor |
| CN107658138B (en) * | 2017-09-13 | 2019-05-31 | 中南大学 | Li6CoO4The preparation method and lithium-ion capacitor of prelithiation agent and lithium-ion capacitor |
| CN107731559B (en) * | 2017-09-13 | 2019-05-31 | 中南大学 | A kind of LiMnO2The preparation method and lithium-ion capacitor of prelithiation agent and lithium-ion capacitor |
| CN107910197B (en) * | 2017-09-28 | 2020-06-09 | 宁波中车新能源科技有限公司 | Lithium ion capacitor and preparation method thereof |
| WO2019200609A1 (en) * | 2018-04-20 | 2019-10-24 | GM Global Technology Operations LLC | Incorporation of lithium-ion source material into an activated carbon electrode for a capacitor-assisted battery |
| CN108766781B (en) * | 2018-05-28 | 2020-05-08 | 浙江微创新能源有限公司 | Positive electrode slurry, positive electrode plate and preparation method of positive electrode plate |
| CN109346335A (en) * | 2018-09-28 | 2019-02-15 | 桑顿新能源科技有限公司 | Lithium source active material, anode pole piece, lithium-ion capacitor and preparation method thereof |
| CN109524653A (en) * | 2018-11-21 | 2019-03-26 | 湖南中车特种电气装备有限公司 | A method of lithium-ion capacitor specific capacity is promoted using conducting polymer |
| CN109545566A (en) * | 2018-11-21 | 2019-03-29 | 湖南中车特种电气装备有限公司 | A kind of high specific energy lithium-ion capacitor |
| CN110400704A (en) * | 2019-06-06 | 2019-11-01 | 宁波中车新能源科技有限公司 | A kind of preparation method and application of hybrid capacitors anode |
| CN111029158B (en) * | 2019-12-22 | 2021-12-17 | 北京蒙京石墨新材料科技研究院有限公司 | Lithium ion supercapacitor lithium pre-embedding method |
| CN112435861B (en) * | 2020-10-16 | 2022-01-11 | 惠州亿纬锂能股份有限公司 | Positive electrode of hybrid capacitor and preparation method and application thereof |
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