CN113921291A - Positive pole piece and lithium ion capacitor - Google Patents

Positive pole piece and lithium ion capacitor Download PDF

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Publication number
CN113921291A
CN113921291A CN202111157062.XA CN202111157062A CN113921291A CN 113921291 A CN113921291 A CN 113921291A CN 202111157062 A CN202111157062 A CN 202111157062A CN 113921291 A CN113921291 A CN 113921291A
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positive
lithium
positive electrode
positive pole
pole piece
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韩徐年
展长振
康辉
赵立川
周杰
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Beijing Mengjing Graphite New Material Science And Technology Research Institute Co ltd
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Beijing Mengjing Graphite New Material Science And Technology Research Institute Co ltd
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    • 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
    • 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
    • H01G11/32—Carbon-based
    • 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
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention provides a positive pole piece and a lithium ion capacitor. The positive pole piece comprises a positive current collector and a positive material, wherein the positive material comprises the following components in percentage by mass: 60.2-84.4% of activated carbon, 8.6-27.9% of ternary positive electrode material, 3-6% of conductive agent and 4-8% of binder. On the basis of adopting active carbon as a main material of the anode material, the ternary anode material is adopted as a lithium source for lithium doping, and the ternary anode material has the characteristics of high energy density, relatively low cost and excellent cycle performance, and particularly has the advantages of higher feasibility of high charging voltage and great high temperature performance and energy density, so that the low-cost, high-efficiency and controllable pre-lithium embedding process can be realized, and the problem of insufficient safety and structural stability is solved. The active carbon material used as the main body of the anode material has low cost and large specific surface area, and can quickly adsorb and desorb lithium ions so as to carry out charging and discharging with ultrahigh power.

Description

Positive pole piece and lithium ion capacitor
Technical Field
The invention relates to the technical field of capacitors, in particular to a positive pole piece and a lithium ion capacitor.
Background
With the widespread application of electric vehicles and large-scale storage battery systems for fixed locations in family and social life, after the transition from nickel-metal hydride batteries to lithium ion batteries of rechargeable batteries is gradually completed, not only the development trend of multiple purposes appears in the development direction of lithium batteries, but also a new electric storage technical route of lithium ion capacitors is created. Lithium batteries operate by chemical reactions with the back-and-forth intercalation and de-intercalation of lithium ions between positive and negative electrodes, so they have a high energy density, but the power density is a short plate. The lithium ion capacitor is an improved variety of the traditional double-electric-layer capacitor, the principle of a negative electrode is the same as that of a lithium ion battery, and the positive electrode utilizes the electrostatic capacity generated by the double-electric-layer effect. Therefore, the lithium ion capacitor not only has the advantages of high power and long service life of the electric double layer capacitor, but also has the characteristic of high capacity of the lithium ion battery. The lithium ion capacitor has a higher energy density than the electric double layer capacitor because the voltage and the capacitance of the cell are increased. This effect is achieved in two ways: (1) the voltage of the capacitor is increased from 2.5V-3V to 4V by adding lithium ions, (2) the negative electrode can obtain lithium ions, so that the capacity of the capacitor is improved by at least 1 time compared with the original activated carbon of the electric double layer capacitor.
The main implementation schemes of the conventional high-performance lithium ion capacitor are as follows:
(1) and a simple substance lithium source is adopted, and lithium is pre-embedded into the negative electrode in modes of electrochemical pre-embedding lithium, internal short circuit, external short circuit and the like. The scheme for pre-embedding lithium by using the elemental lithium source is difficult to control the doping amount of lithium, is easy to generate potential safety hazards such as volume change, short circuit, thermal runaway and the like, and consumes a large amount of time when pre-embedding lithium by using the elemental lithium source.
(2) The positive electrode incorporates conventional lithium ion battery positive electrode materials (including but not limited to LiFePO)4、LiCoO2、LiMn2O4Lithium rich manganese based, etc.). By doping conventional lithium into the positive electrodeThe realization scheme of the anode material of the ion battery has the serious restriction of LiCoO due to the fact that the monopoly price of the metal cobalt is increasingly soared2Use in energy storage devices, and LiFePO4、LiMn2O4The capacity exertion is low, the requirement of pursuing high-energy mobile phone batteries at present is not suitable, the lithium-rich manganese base is also in the research and development stage, and the practical application is early.
(3) The positive electrode incorporates a lithium-rich and irreversibly delithiated lithium salt (including, but not limited to, Li)5FeO4、Li2HBN, etc.) to insert lithium doped with lithium salt irreversibly into the negative electrode during the first cycle, thereby achieving the purpose of pre-inserting lithium. Among them, some of the remaining part after the first cycle loses activity and becomes an ineffective component, some of the remaining part escapes in a gas form or is dissolved in an electrolyte, and no longer contributes to capacity to cause energy density reduction, the used lithium salt has high environmental requirements, and if large-scale production is to be performed, environmental control cost is relatively high, and in addition, there is a possibility of side reactions.
Disclosure of Invention
The invention mainly aims to provide a positive pole piece and a lithium ion capacitor, and aims to solve the problem that the safety and the structural stability of the lithium ion capacitor in the prior art are insufficient.
In order to achieve the above object, according to one aspect of the present invention, there is provided a positive electrode sheet including a positive electrode current collector and a positive electrode material, the positive electrode material including, by mass: 60.2-84.4% of activated carbon; 8.6-27.9% of a ternary positive electrode material; 3-6% of a conductive agent; 4-8% of a binder.
Further, the ternary positive electrode material is selected from one or more of NCM424, NCM333, and NCM 523.
Further, the conductive agent is selected from any one or more of carbon nanotubes, conductive graphite ks6 and graphene, and preferably the conductive agent is selected from the group consisting of carbon nanotubes, conductive graphite ks6 and graphene in a ratio of 1-2: 1-2: 1-2 by mass ratio.
Further, the binder is selected from one or more of PVDF, CMC, PVA, PTFE, LA series and polyimide, and preferably the binder is selected from a mixture of PVDF and polyimide mixed in a mass ratio of 1: 2-2: 1.
Further, the positive electrode current collector is selected from any one of carbon-coated aluminum foil, foamed nickel, polished aluminum foil and corroded aluminum foil, and the surface density of the positive electrode plate is preferably 80-120 g/m2。
According to another aspect of the present invention, there is provided a lithium ion capacitor, including a positive electrode plate, a separator, a negative electrode plate, and an electrolyte, where the positive electrode plate is any one of the positive electrode plates described above.
Further, the negative pole piece comprises a negative pole current collector and a negative pole material, wherein the negative pole material comprises a conductive agent, a negative pole main material and a binder, the mass content of the conductive agent is 2-4%, the mass content of the negative pole main material is 92-96%, and the mass content of the binder is 2-4%.
Further, the main material of the negative electrode is selected from any one or more of graphite, mesocarbon microbeads, soft carbon and hard carbon.
Further, the electrolyte of the electrolyte is selected from LiBF4、LiAsF6、LiCF3SO3、LiFP6、LiClO4Any one or more of them.
By applying the technical scheme of the invention, the ternary cathode material is adopted as the lithium source for lithium doping on the basis of adopting the active carbon as the main material of the cathode material, and the ternary cathode material has the characteristics of high energy density, relatively low cost and excellent cycle performance, and particularly has the advantages of higher feasibility of high charging voltage and great high-temperature performance and energy density, so that the low-cost, high-efficiency and controllable pre-lithium intercalation process can be realized, and the problems of insufficient safety and structural stability are solved. And the addition amount of the added ternary cathode material can be elastically adjusted according to the capacity requirement, so that the doping amount of lithium can be accurately controlled. And the active carbon material used as the main body of the anode material has low cost and large specific surface area, and can quickly adsorb and desorb lithium ions so as to carry out charging and discharging with ultrahigh power (more than or equal to 2 kW/kg).
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background of the present application, the safety and structural stability of the prior art lithium ion capacitors are insufficient. In order to solve the problem, the application provides a positive pole piece and a lithium ion capacitor.
In an exemplary embodiment of the present application, there is provided a positive electrode sheet, including a positive electrode current collector and a positive electrode material, wherein the positive electrode material includes, by mass: 60.2-84.4% of activated carbon, 8.6-27.9% of ternary positive electrode material, 3-6% of conductive agent and 4-8% of binder.
This application adopts the ternary cathode material to dope lithium as the lithium source on the basis of adopting activated carbon as the host material of cathode material, because ternary cathode material has the characteristics that energy density is high, the cost is lower relatively, the cycle performance is excellent, especially has that the feasibility of high charging voltage is higher, high temperature performance and energy density have very big advantage, consequently can realize low-cost, high-efficient and controllable lithium process of inlaying in advance, solves such as aforementioned security and the not enough problem of structural stability. And the addition amount of the added ternary cathode material can be elastically adjusted according to the capacity requirement, so that the doping amount of lithium can be accurately controlled. And the active carbon material used as the main body of the anode material has low cost and large specific surface area, and can quickly adsorb and desorb lithium ions so as to carry out charging and discharging with ultrahigh power (more than or equal to 2 kW/kg).
The ternary cathode material used in the present application is mainly for providing lithium ions, and a conventional ternary cathode material or a ternary cathode material prepared by a known method can be considered to be used in the present application, and in some embodiments, the ternary cathode material is selected from any one or more of NCM424, NCM333, and NCM523, and the ternary cathode material is a ternary cathode material with higher performance at present, and can be used in the present application regardless of a base product or a doped or coated product thereof.
In some embodiments, the conductive agent is selected from any one or more of carbon nanotubes, conductive graphite ks6 and graphene, preferably the conductive agent is selected from carbon nanotubes, conductive graphite ks6 and graphene in a ratio of 1-2: 1-2: 1-2 mass ratio; the linear carbon nano-particles and the flaky graphene are used for constructing a three-dimensional conductive network, and the heat dissipation performance of the conductive graphite ks6 is combined, so that the energy density of the capacitor is further improved, and the ultrahigh-power charging and discharging can be further carried out.
In some embodiments, the binder is selected from any one or more of PVDF, CMC, PVA, PTFE, LA series and polyimide, preferably, the binder is selected from a mixture of PVDF and polyimide mixed in a mass ratio of 1:2 to 2:1, the toughness of PVDF is used to ensure that the positive electrode materials are connected with each other in a following manner during charging and discharging, and the rigidity of polyimide is used to ensure that the positive electrode materials do not separate from the current collector under ultrahigh power. The positive current collector used in the present application is an aluminum foil with a conductive carbon layer coated on the surface of the aluminum foil. Because the active carbon has low compacted density and the ternary anode material has high compacted density, the difference between the two is too large, and the two are balanced, the surface density of the anode piece can be 80g/m2～120g/m2Preferably, the surface density of the positive pole piece is 95g/m2～105g/m2。
The preparation of the positive electrode plate of the present application can be realized by adopting a conventional preparation process of the positive electrode plate, and the preparation process of the positive electrode plate is briefly described below, but those skilled in the art should understand that the description is an exemplary description of the preparation process of the positive electrode plate, and should not be understood as the preparation of the positive electrode plate can only be realized by adopting the following preparation process.
Weighing 60.2-84.4% of activated carbon, 8.6-27.9% of ternary positive electrode material, 3-6% of conductive agent and 2-8% of binder;
preparing a mixed glue solution of a binder and a solvent by adopting a stirring or ball milling process, wherein the solid content of the glue solution is 3-8%;
adding weighed active carbon, ternary materials and conductive agents into the glue solution, and uniformly dispersing by adopting a stirring or ball milling process to obtain slurry dispersion liquid suitable for coating;
and uniformly coating the slurry dispersion liquid on a current collector to obtain the positive pole piece.
In another exemplary embodiment of the present application, there is also provided a lithium ion capacitor, including a positive electrode plate, a separator, a negative electrode plate, and an electrolyte, where the positive electrode plate is any one of the positive electrode plates described above.
Because the positive pole piece of this application adopts the active carbon as the host material of positive pole material, adopts ternary positive pole material to mix lithium as the lithium source, has the characteristics that energy density is high, the cost is relatively lower, the cycle performance is excellent based on ternary positive pole material, and especially has that the feasibility of high charging voltage is higher, high temperature performance and energy density have very big advantage, consequently can realize low-cost, high-efficient and controllable lithium process of inlaying in advance, solves the not enough problem of security and the structural stability of positive pole piece. And the active carbon material used as the main body of the anode material has low cost and large specific surface area, and can quickly adsorb and desorb lithium ions so as to carry out charging and discharging with ultrahigh power (more than or equal to 2 kW/kg). The addition amount of the added ternary cathode material can be flexibly adjusted according to the capacity requirement, and further the doping amount of lithium can be accurately controlled. Therefore, the lithium ion capacitor with the positive pole piece has the characteristics of high safety, stable structure and high energy density.
In order to match with the positive pole piece and improve the capacity of the capacitor, the negative pole piece preferably comprises a negative current collector and a negative material, the negative material comprises a conductive agent, a negative main material and a binder, the mass content of the conductive agent is 2-4%, the mass content of the negative main material is 92-96%, and the mass content of the binder is 2-4%.
The negative electrode main material used for the negative electrode sheet of the present application includes, but is not limited to, any one or more of graphite, mesocarbon microbeads, soft carbon, and hard carbon. The binder and the conductive agent can adopt corresponding substance types commonly used in the prior art, and are not described in detail in the application.
In some embodiments of the present application, the electrolyte of the electrolyte is selected from LiBF4、LiAsF6、LiCF3SO3、LiFP6、LiClO4Any one or more of them. The electrolyte can be rapidly adsorbed and desorbed with the active carbon and can be used for releasing and embedding lithium in the ternary material.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
Preparing a positive plate:
(1) weighing: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g of conductive graphite ks, 1g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP (solvent is volatilized after coating);
(2) preparing glue solution: putting 2g of weighed PDVF, 2g of polyimide and 96g of NMP into a planetary mixer, revolving at 30RPM, rotating at 1200RPM, stirring for 3h, vacuumizing for 0.5h, and keeping the vacuum degree at 100 pa;
(3) homogenizing: adding 27.9g of weighed ternary materials, 65.1g of activated carbon, 1g of carbon nano tube, 61g of conductive graphite and 1g of graphene into glue solution, revolving at 45RPM, rotating at 1500RPM, stirring for 6h, vacuumizing for 0.5h, and keeping the vacuum degree at 100 pa;
(4) coating: coating the slurry obtained in the step (3) on a carbon-coated aluminum foil to obtain the surface density of 95g/m2Is a positive electrode plate;
(5) rolling: putting the pole piece obtained in the step (4) into a roller press for rolling, and compacting to 1.0g/cm3；
(6) Tabletting: and (4) cutting the positive electrode plate obtained in the step (5) into a circular sheet with the diameter of 14mm for later use.
Example 2
The difference from example 1 is that the composition of the positive electrode material is: 8.6g of ternary material (NCM523), 84.4g of activated carbon, 1g of carbon nanotube, 61g g of conductive graphite ks, 1g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 3
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 60.2g of activated carbon, 2g of carbon nanotube, 62g g of conductive graphite ks, 2g of graphene, 3g of PDVF, 2.9g of polyimide and 96g of NMP.
Example 4
The difference from example 1 is that the composition of the positive electrode material is: 23.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g g of conductive graphite ks, 1g of graphene, 4g of PDVF, 4g of polyimide and 96g of NMP.
Example 5
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 1.5g of carbon nanotube, 61.5g of conductive graphite ks61, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 6
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 61.5g of conductive graphite ks61, 1.5g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 7
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 1.5g of carbon nanotube, 1.5g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 8
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g of conductive graphite ks, 1g of graphene, 4g of PDVF and 96g of NMP.
Example 9
The difference from example 1 is that the composition of the positive electrode material is: 27.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g of conductive graphite ks, 1g of graphene, 4g of polyimide and 96g of NMP.
Example 10
The difference from example 1 is that the composition of the positive electrode material is: 26.9g of ternary material (NCM523), 65.1g of activated carbon, 2g of carbon nanotube, 61g g of conductive graphite ks, 1g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 11
The difference from example 1 is that the composition of the positive electrode material is: 26.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 62g of conductive graphite ks, 1g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 12
The difference from example 1 is that the composition of the positive electrode material is: 24.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 62g g of conductive graphite ks, 3g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP.
Example 13
The difference from example 1 is that the composition of the positive electrode material is: 25.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g of conductive graphite ks, 1g of graphene, 4g of PDVF, 2g of polyimide and 96g of NMP.
Example 14
The difference from example 1 is that the composition of the positive electrode material is: 25.9g of ternary material (NCM523), 65.1g of activated carbon, 1g of carbon nanotube, 61g g of conductive graphite ks, 1g of graphene, 2g of PDVF, 4g of polyimide and 96g of NMP.
Comparative example 1
Preparing a positive plate:
(1) weighing: weighing 93g of activated carbon, 1g of carbon nano tube, 61g g of conductive graphite ks, 1g of graphene, 2g of PDVF, 2g of polyimide and 96g of NMP;
(2) preparing glue solution: putting 2g of weighed PDVF, 2g of polyimide and 96g of NMP into a planetary mixer, revolving at 30RPM, rotating at 1200RPM, stirring for 3h, vacuumizing for 0.5h, and keeping the vacuum degree at 100 pa;
(3) homogenizing: adding 93g of weighed activated carbon, 1g of carbon nano tube, 61 ks of conductive graphite 61g and 1g of graphene into the glue solution, revolving at 45RPM, rotating at 1500RPM, stirring for 6h, and vacuumizing for 0.5h, wherein the vacuum degree is 100 pa;
(4) coating: coating the slurry obtained in the step (3) on a carbon-coated aluminum foil to obtain the surface density of 95g/m2Is a positive electrode plate;
(5) rolling: putting the pole piece obtained in the step (4) into a roller press for rolling, and compacting to 1.0g/cm3；
(6) Tabletting: and (4) cutting the positive electrode plate obtained in the step (5) into a circular sheet with the diameter of 14mm for later use.
Preparing a battery:
preparing a negative plate:
(1) weighing: weighing 96g of soft carbon, SP 2g of conductive carbon black, PVDF2g and NMP 98 g;
(2) preparing glue solution: putting 2g of weighed PDVF and 98g of NMP into a planetary stirrer, revolving at 30RPM, rotating at 1200RPM, stirring for 3h, vacuumizing for 0.5h, and keeping the vacuum degree at 100 pa;
(3) homogenizing: adding 96g of weighed soft carbon and SP 2g of conductive carbon black into the glue solution, revolving at 45RPM, rotating at 1500RPM, stirring for 6h, vacuumizing for 0.5h, and keeping the vacuum degree at 100 pa;
(4) coating: putting the slurry obtained in the step (3) into a trough of a coating machine, wherein the tape moving speed of the coating machine is 5m/min, the air frequency of an oven of the coating machine is 75Hz, and the temperature of the oven is 90 ℃, so that the surface density is 9g/m2Is a negative electrode plate;
(5) rolling: putting the negative pole piece obtained in the step (4) into a roller press for rolling, and compacting to 1.0g/cm3；
(6) Tabletting: and (4) cutting the negative electrode plate obtained in the step (5) into a wafer with the diameter of 14mm for later use.
Assembling a sample:
(1) preparing positive and negative electrode wafers with the diameter of 14 mm;
(2) preparing a positive and negative electrode shell, a gasket and an elastic sheet which are matched with the CR2025 in the assembling process;
(3) preparing electrolyte used in an assembly process, wherein the electrolyte comprises the components of LiPF6/DC + EMC;
(4) preparing a PP/PE septum for use in an assembly process;
(5) assembling a sample according to the sequence of the positive electrode shell, the positive electrode plate, the electrolyte, the diaphragm, the electrolyte, the negative electrode plate, the gasket, the elastic sheet and the negative electrode shell;
(6) sealing the assembled sample using a CR2025 button sealer;
(7) standing the assembled sample for 24h, and then, activating and testing;
sample activation and testing:
(1) electrochemical activation of the capacitor comprising each example and comparative example was performed using a 0.1C current;
(2) carrying out constant-current charge and discharge test on the sample by using 3C current;
the energy densities and power densities of the examples and comparative examples are shown in Table 1
As can be seen from Table 1, the examples show a large increase in both energy density and power density relative to the comparative examples.
TABLE 1 energy Density and Power Density test results
Figure BDA0003288676020000071
Figure BDA0003288676020000081
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
this application adopts the ternary cathode material to dope lithium as the lithium source on the basis of adopting activated carbon as the host material of cathode material, because ternary cathode material has the characteristics that energy density is high, the cost is lower relatively, the cycle performance is excellent, especially has that the feasibility of high charging voltage is higher, high temperature performance and energy density have very big advantage, consequently can realize low-cost, high-efficient and controllable lithium process of inlaying in advance, solves such as aforementioned security and the not enough problem of structural stability. And the addition amount of the added ternary cathode material can be elastically adjusted according to the capacity requirement, so that the doping amount of lithium can be accurately controlled. And the active carbon material used as the main body of the anode material has low cost and large specific surface area, and can quickly adsorb and desorb lithium ions so as to carry out charging and discharging with ultrahigh power (more than or equal to 2 kW/kg).
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A positive pole piece comprises a positive pole current collector and a positive pole material, and is characterized in that the positive pole material comprises the following components in percentage by mass:
Figure FDA0003288676010000011
2. the positive electrode sheet according to claim 1, wherein the ternary positive electrode material is selected from one or more of NCM424, NCM333 and NCM 523.
3. The positive pole piece according to claim 1 or 2, wherein the conductive agent is selected from any one or more of carbon nanotubes, conductive graphite ks6 and graphene, preferably the conductive agent is selected from carbon nanotubes, conductive graphite ks6 and graphene in a ratio of 1-2: 1-2: 1-2 by mass ratio.
4. The positive electrode plate as claimed in claim 1 or 2, wherein the binder is selected from any one or more of PVDF, CMC, PVA, PTFE, LA series and polyimide, preferably the binder is selected from a mixture of PVDF and polyimide mixed in a mass ratio of 1: 2-2: 1.
5. The positive pole piece according to claim 1 or 2, wherein the positive current collector is selected from any one of carbon-coated aluminum foil, foamed nickel, polished aluminum foil and corroded aluminum foil, and preferably the surface density of the positive pole piece is 80-120 g/m2。
6. A lithium ion capacitor, comprising a positive electrode plate, a diaphragm, a negative electrode plate and an electrolyte, wherein the positive electrode plate is the positive electrode plate of any one of claims 1 to 5.
7. The lithium ion capacitor of claim 6, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode material, the negative electrode material comprises a conductive agent, a negative electrode main material and a binder, the conductive agent is 2-4% by mass, the negative electrode main material is 92-96% by mass, and the binder is 2-4% by mass.
8. The lithium ion capacitor according to claim 7, wherein the negative electrode main material is selected from any one or more of graphite, mesocarbon microbeads, soft carbon and hard carbon.
9. The li-ion capacitor of claim 7, wherein the electrolyte of the electrolyte is selected from LiBF4、LiAsF6、LiCF3SO3、LiFP6、LiClO4Any one or more of them.
CN202111157062.XA 2021-09-30 2021-09-30 Positive pole piece and lithium ion capacitor Pending CN113921291A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101079510A (en) * 2007-06-25 2007-11-28 中南大学 A super capacitance cell
CN105336504A (en) * 2015-09-24 2016-02-17 宁波南车新能源科技有限公司 Hybrid capacitor battery
CN112289592A (en) * 2020-09-17 2021-01-29 中国科学院山西煤炭化学研究所 Lithium ion capacitor and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101079510A (en) * 2007-06-25 2007-11-28 中南大学 A super capacitance cell
CN105336504A (en) * 2015-09-24 2016-02-17 宁波南车新能源科技有限公司 Hybrid capacitor battery
CN112289592A (en) * 2020-09-17 2021-01-29 中国科学院山西煤炭化学研究所 Lithium ion capacitor and preparation method thereof

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