CN113593920A - Lithium ion capacitor negative pole piece and preparation method thereof - Google Patents
Lithium ion capacitor negative pole piece and preparation method thereof Download PDFInfo
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- CN113593920A CN113593920A CN202110907508.XA CN202110907508A CN113593920A CN 113593920 A CN113593920 A CN 113593920A CN 202110907508 A CN202110907508 A CN 202110907508A CN 113593920 A CN113593920 A CN 113593920A
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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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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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
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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
- H01G11/32—Carbon-based
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
本发明涉及一种锂离子电容器负极极片及其制备方法。该锂离子电容器包括：叠片式电芯、电解液和电容器壳体；所述叠片式电芯包括正极极片、预嵌锂隔膜和负极极片；所述负极极片中包括负极集流体和负极活性层，所述负极集流体采用微孔金属箔，能够有效的承载电极活性物质，加快电荷的传输速率，减少电化学极化内阻；负极活性层由碳材料、导电剂和粘结剂水溶液按特定配比配置而成，获得柔性较佳的极片，一方面能够保证在制备电容器单体时，不掉料、不起皮保证单体不会短路；另一方面能够提高离子的快速传输，提高单体的倍率性能。
The invention relates to a negative pole piece of a lithium ion capacitor and a preparation method thereof. The lithium ion capacitor includes: a laminated cell, an electrolyte and a capacitor casing; the laminated cell includes a positive pole piece, a pre-embedded lithium separator and a negative pole piece; the negative pole piece includes a negative electrode current collector and the negative electrode active layer, the negative electrode current collector is made of microporous metal foil, which can effectively carry the electrode active material, accelerate the transfer rate of charges, and reduce the internal resistance of electrochemical polarization; the negative electrode active layer is composed of carbon materials, conductive agents and adhesives. The aqueous solution is configured according to a specific ratio to obtain a pole piece with better flexibility. On the one hand, it can ensure that when the capacitor monomer is prepared, the material will not drop or peel to ensure that the monomer will not be short-circuited; on the other hand, it can improve the ionic conductivity. Fast transmission, improving the rate performance of the monomer.
Description
Technical Field
The invention relates to the technical field of energy storage devices, in particular to a lithium ion capacitor negative pole piece and a preparation method thereof.
Background
The lithium ion capacitor is an energy storage device between a lithium ion battery and a super capacitor, a capacitive anode material and a battery-characteristic cathode material are adopted, and the selection of the anode and cathode and the electrolyte material and the effect of pre-embedding lithium in the cathode of the lithium ion capacitor are of great importance to the influence of the electrochemical performance of the lithium ion capacitor;
the development of the lithium ion capacitor has been in recent 30 years, the performances of positive and negative active substances, such as activated carbon, graphite, lithium titanium oxide and other materials, of the lithium ion capacitor tend to be stable, and the requirements of the industry on the performances of key materials of the lithium ion capacitor can be met; therefore, the pre-embedded ring section of the negative electrode lithium in the lithium ion capacitor system becomes a key parameter for realizing the high-performance lithium ion capacitor, and what material is adopted by the current collector in the lithium ion capacitor is a key of the pre-embedded link, so that the prepared negative electrode plate which is beneficial to pre-embedded lithium has a vital function for realizing the low internal resistance of the lithium ion capacitor.
Disclosure of Invention
The invention aims to provide a lithium ion capacitor negative pole piece and a preparation method thereof, and solves the problems that the conventional negative pole piece has high internal resistance and has adverse influence on the assembly of a high-performance lithium ion capacitor.
In order to achieve the purpose, the invention provides the following scheme:
a negative electrode sheet of a lithium ion capacitor, comprising:
a negative electrode current collector and a negative electrode active layer coated on the negative electrode current collector;
the negative current collector is a microporous metal foil, and the surface of the negative current collector is provided with a plurality of through holes.
Optionally, the microporous metal foil is one of rolled copper foil or electrolytic copper foil, the aperture is in the range of 10-30 μm, the thickness is 8-20 μm, and the density of through holes thereon is 1000/cm2。
Optionally, the negative active layer includes a negative active layer slurry, and the negative active layer slurry includes a carbon material, a conductive agent, and a binder.
Optionally, the thickness of the slurry of the negative active layer is 30-50 μm, the mass fraction ratio of the slurry is 6-20% of a conductive agent, 2-10% of a binder and 70-92% of a carbon material, and the sum of the mass fraction ratios of the conductive agent, the binder and the carbon material is 100%;
optionally, the carbon material is at least one of soft carbon, hard carbon, mesocarbon microbeads and graphite.
Optionally, the conductive agent is one or a mixture of several of ketjen black, acetylene black, graphene and carbon nanotubes.
Optionally, the binder is one or a mixture of several of polyvinylidene fluoride, ethylene acrylic acid, ethylene vinyl acetate, styrene butadiene rubber and carboxymethyl cellulose.
The invention also provides a preparation method of the negative pole piece, which comprises the following steps:
a1, determining the proportion of the slurry of the negative active layer;
a2, preparing the anode active layer slurry according to the proportion;
and A3, uniformly coating the negative active layer slurry on a negative current collector, wherein the negative current collector is a microporous metal foil.
Further, the present invention also provides a lithium ion capacitor, including: the laminated battery cell comprises a laminated battery cell, electrolyte and a capacitor shell, wherein the electrolyte and the laminated battery cell are arranged in the capacitor shell;
the laminated battery cell comprises a negative pole piece, a pre-embedded lithium diaphragm and a positive pole piece which are sequentially stacked, wherein the negative pole piece is prepared by the above steps.
Correspondingly, the invention also provides a preparation method of the lithium ion capacitor, which comprises the following steps:
b1, preparing a negative pole piece according to the preparation method of the negative pole piece;
b2, rolling and cutting the negative pole piece;
b3, stacking the cut negative pole piece, the pre-embedded lithium diaphragm and the positive pole piece into a laminated battery cell;
b4, placing the laminated battery core into a capacitor shell for sealing, wherein the capacitor shell is an aluminum-plastic film;
and B5, injecting electrolyte into the capacitor shell and forming.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
according to the lithium ion capacitor negative pole piece and the preparation method thereof, the negative current collector adopts the microporous metal foil, so that the negative current collector can effectively bear electrode active substances, the charge transmission rate is increased, and the electrochemical polarization internal resistance is reduced; the negative active layer is prepared from a carbon material, a conductive agent and a binder aqueous solution according to a specific ratio, so that a pole piece with good flexibility is obtained, and on one hand, the material falling and peeling can be avoided when the capacitor monomer is prepared, and the monomer can not be short-circuited; on the other hand, the rapid transmission of ions can be improved, and the rate capability of the monomer is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a negative electrode tab according to embodiment 1 of the present invention;
fig. 2 is a flowchart of a method for manufacturing a negative electrode tab according to embodiment 2 of the present invention;
fig. 3 is a schematic structural diagram of a lithium ion capacitor provided in embodiment 3 of the present invention;
fig. 4 is a flowchart of a method for manufacturing a lithium ion capacitor according to embodiment 4 of the present invention.
Symbol interpretation:
1: a lithium ion capacitor; 2: a capacitor case; 3: an electrolyte; 4: a laminated cell; 5: a positive electrode plate; 6: pre-embedding a lithium diaphragm; 7: a negative pole piece; 8: a negative current collector; 9: and a negative electrode active layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a lithium ion capacitor negative pole piece and a preparation method thereof, and solves the problems that the conventional negative pole piece has high internal resistance and has adverse influence on the assembly of a high-performance lithium ion capacitor.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1:
as shown in fig. 1, the present invention provides a negative electrode tab, which includes:
a negative electrode current collector 8 and a negative electrode active layer 9 coated on the negative electrode current collector 8;
the negative current collector 8 is a microporous metal foil, and the surface thereof is provided with a plurality of through holes.
The thickness of the negative current collector 8 is 8-20 μm, and the density of the through holes is 1000/cm2The pore diameter is within the range of 10-30 μm.
In some embodiments, the microporous metal foil is one of a rolled copper foil or an electrolytic copper foil.
In specific implementation, the negative active layer 9 comprises negative active layer slurry with the thickness of 30-50 μm, wherein the slurry comprises a carbon material, a conductive agent and a binder; the carbon material is at least one of soft carbon, hard carbon, mesocarbon microbeads and graphite, the conductive agent is one or a mixture of more of Ketjen black, acetylene black, graphene and carbon nanotubes, and the binder is one or a mixture of more of polyvinylidene fluoride, ethylene acrylic acid, ethylene vinyl acetate, styrene butadiene rubber and carboxymethyl cellulose.
In some embodiments, the mass fraction ratio of the negative active layer slurry is 6-20% of the conductive agent, 2-10% of the binder and 70-92% of the carbon material, and the sum of the mass fraction ratios of the conductive agent, the binder and the carbon material is 100%.
Example 2:
as shown in fig. 2, the invention also provides a preparation method of the negative electrode plate, which comprises the following steps:
a1, determining the proportion of the slurry of the negative active layer 9;
a2, preparing the anode active layer slurry according to the proportion;
and A3, uniformly coating the negative active layer slurry on a negative current collector 8, wherein the negative current collector 8 is a microporous metal foil.
Example 3:
as shown in fig. 3, the present invention also provides a lithium ion capacitor to which the negative electrode tab of embodiment 1 is applied, the lithium ion capacitor including:
the laminated battery cell comprises a laminated battery cell 4, electrolyte 3 and a capacitor shell 2; the electrolyte 3 and the laminated battery cell 4 are arranged inside the capacitor shell 2;
the laminated battery cell 4 comprises a negative pole piece 7, a pre-embedded lithium diaphragm 6 and a positive pole piece 5 which are sequentially laminated.
Example 4:
as shown in fig. 4, the present invention further provides a method for manufacturing a lithium ion capacitor, including the following steps:
b1, preparing the negative pole piece 7 according to the preparation method of the negative pole piece 7;
b2, rolling and cutting the negative pole piece 7;
b3, stacking the cut negative pole piece 7, the pre-embedded lithium diaphragm 6 and the positive pole piece 5 into a laminated battery core 4;
b4, placing the laminated battery cell 4 into a capacitor shell 2 for sealing, wherein the capacitor shell 2 is an aluminum-plastic film;
b5, the electrolytic solution 3 is injected into the capacitor case 2 and formed.
Example 5:
in order to show that the lithium ion capacitor prepared by the preparation method of the lithium ion capacitor has good performance, different lithium ion capacitors are prepared according to the negative electrode current collectors with different sizes and apertures and different negative electrode active layer slurry proportions respectively, and performance tests are carried out.
Sample one:
determining the proportion of the slurry of the cathode active layer 9, and adopting the mass fraction ratio of 3% of binder, 87% of carbon material and 10% of conductive agent;
preparing cathode active layer slurry according to a determined proportion, adding 3% of binder into ultrapure water, stirring for a certain time to completely dissolve, adding 87% of carbon material and 10% of conductive agent, and uniformly stirring to obtain cathode active layer slurry;
and uniformly coating the slurry of the negative active layer on a negative current collector 8, wherein the negative current collector 8 is a microporous copper foil, the aperture of the microporous copper foil is about 15 mu m, coating the slurry of the negative active layer on the microporous copper foil current collector, and drying for later use.
Rolling and cutting the prepared negative pole piece 7 into a proper size;
stacking the cut negative pole piece 7, the pre-embedded lithium diaphragm 6 and the positive pole piece 5 into a laminated battery cell 4;
wrapping and sealing the laminated battery cell 4 by using an aluminum plastic film to form a capacitor shell 2;
an electrolyte 3 is injected into the capacitor case 2 and formed, and a first lithium ion capacitor sample is prepared.
Sample two:
determining the proportion of the slurry of the cathode active layer 9, and adopting the mass fraction ratio of 6% of binder, 86% of carbon material and 8% of conductive agent;
preparing cathode active layer slurry according to a determined proportion, adding 6% of binder into ultrapure water, stirring for a certain time to completely dissolve, adding 86% of carbon material and 8% of conductive agent, and uniformly stirring to obtain cathode active layer slurry;
and uniformly coating the slurry of the negative active layer on a negative current collector 8, wherein the negative current collector 8 is a microporous copper foil, the aperture of the microporous copper foil is about 15 mu m, coating the slurry of the negative active layer on the microporous copper foil current collector, and drying for later use.
Rolling and cutting the prepared negative pole piece 7 into a proper size;
stacking the cut negative pole piece 7, the pre-embedded lithium diaphragm 6 and the positive pole piece 5 into a laminated battery cell 4;
wrapping and sealing the laminated battery cell 4 by using an aluminum plastic film to form a capacitor shell 2;
an electrolyte 3 was injected into the capacitor case 2 and formed into a lithium ion capacitor sample two.
Sample three:
determining the proportion of the slurry of the cathode active layer 9, and adopting the mass fraction ratio of 3% of binder, 87% of carbon material and 10% of conductive agent;
preparing cathode active layer slurry according to a determined proportion, adding 3% of binder into ultrapure water, stirring for a certain time to completely dissolve, adding 87% of carbon material and 10% of conductive agent, and uniformly stirring to obtain cathode active layer slurry;
and uniformly coating the slurry of the negative active layer on a negative current collector 8, wherein the negative current collector 8 is a microporous copper foil, the aperture of the microporous copper foil is about 25 mu m, coating the slurry of the negative active layer on the microporous copper foil current collector, and drying for later use.
Rolling and cutting the prepared negative pole piece 7 into a proper size;
stacking the cut negative pole piece 7, the pre-embedded lithium diaphragm 6 and the positive pole piece 5 into a laminated battery cell 4;
wrapping and sealing the laminated battery cell 4 by using an aluminum plastic film to form a capacitor shell 2;
an electrolyte 3 was injected into the capacitor case 2 and formed into a lithium ion capacitor sample three.
Sample four:
determining the proportion of the slurry of the cathode active layer 9, and adopting the mass fraction ratio of 6% of binder, 86% of carbon material and 8% of conductive agent;
preparing cathode active layer slurry according to a determined proportion, adding 6% of binder into ultrapure water, stirring for a certain time to completely dissolve, adding 86% of carbon material and 8% of conductive agent, and uniformly stirring to obtain cathode active layer slurry;
and uniformly coating the slurry of the negative active layer on a negative current collector 8, wherein the negative current collector 8 is a microporous copper foil, the aperture of the microporous copper foil is about 25 mu m, coating the slurry of the negative active layer on the microporous copper foil current collector, and drying for later use.
Rolling and cutting the prepared negative pole piece 7 into a proper size;
stacking the cut negative pole piece 7, the pre-embedded lithium diaphragm 6 and the positive pole piece 5 into a laminated battery cell 4;
wrapping and sealing the laminated battery cell 4 by using an aluminum plastic film to form a capacitor shell 2;
an electrolyte 3 was injected into the capacitor case 2 and the mixture was formed to prepare a lithium ion capacitor sample four.
Sample preparation index parameters:
the mixing time, the slurry viscosity, the slurry fineness and the roll-in density parameters of the slurry when the lithium ion capacitor is prepared are shown in table 1:
TABLE 1 preparation of index parameters
And (3) comparing test results:
the comparison results of the internal resistance and the rate capability of the lithium ion capacitor sample I, the lithium ion capacitor sample II, the lithium ion capacitor sample III and the lithium ion capacitor sample IV are shown in the table 2.
TABLE 2 comparison of internal resistance and rate capability
According to the lithium ion capacitor negative pole piece and the preparation method thereof, the negative current collector adopts the microporous metal foil, so that the negative current collector can effectively bear electrode active substances, the charge transmission rate is increased, and the electrochemical polarization internal resistance is reduced; the negative active layer is prepared from a carbon material, a conductive agent and a binder aqueous solution according to a specific ratio, so that a pole piece with good flexibility is obtained, and on one hand, the material falling and peeling can be avoided when the capacitor monomer is prepared, and the monomer can not be short-circuited; on the other hand, the rapid transmission of ions can be improved, and the rate capability of the monomer is improved.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. A negative electrode tab, comprising:
a negative electrode current collector and a negative electrode active layer coated on the negative electrode current collector;
the negative current collector is a microporous metal foil, and the surface of the negative current collector is provided with a plurality of through holes.
2. The negative electrode tab of claim 1, wherein the microporous metal foil is one of a rolled copper foil or an electrolytic copper foil.
3. The negative electrode plate as claimed in claim 1, wherein the thickness of the microporous metal foil is 8-20 μm, and the density of the through holes is 1000/cm2The diameter of the through hole is 10 to 30 μm.
4. The negative electrode tab of claim 1, wherein the negative active layer comprises a negative active layer slurry;
the thickness of the slurry of the negative active layer is 30-50 mu m, and the slurry comprises a carbon material, a conductive agent and a binder; in the negative active layer slurry, a conductive agent accounts for 6-20%, a binder accounts for 2-10%, a corresponding carbon material accounts for 70-92%, and the sum of the mass fractions of the conductive agent, the binder and the carbon material is 100%.
5. The negative electrode tab of claim 4, wherein the carbon material is at least one of soft carbon, hard carbon, mesocarbon microbeads and graphite.
6. The negative electrode plate as claimed in claim 4, wherein the conductive agent is one or more of Ketjen black, acetylene black, graphene and carbon nanotubes.
7. The negative electrode plate as claimed in claim 4, wherein the binder is one or more of polyvinylidene fluoride, ethylene acrylic acid, ethylene vinyl acetate, styrene butadiene rubber and carboxymethyl cellulose.
8. A preparation method of a negative pole piece is characterized by comprising the following steps:
determining the proportion of the slurry of the negative active layer;
preparing the anode active layer slurry according to the proportion;
and uniformly coating the negative active layer slurry on a negative current collector, wherein the negative current collector is a microporous metal foil.
9. A lithium ion capacitor, comprising: the laminated battery cell comprises a laminated battery cell, electrolyte and a capacitor shell; the laminated battery cell comprises a negative pole piece, a pre-embedded lithium diaphragm and a positive pole piece which are sequentially laminated, wherein the negative pole piece is the negative pole piece in claim 1; the electrolyte and the laminated battery cell are arranged inside a capacitor shell.
10. A method for manufacturing a lithium ion capacitor is characterized by comprising the following steps:
preparing a negative pole piece according to the preparation method of the negative pole piece of claim 8;
rolling and cutting the negative pole piece;
stacking the rolled and cut negative pole piece, the pre-embedded lithium diaphragm and the positive pole piece in sequence to form a laminated battery cell;
putting the laminated cell into a capacitor shell for sealing, wherein the capacitor shell is an aluminum-plastic film;
and injecting electrolyte into the capacitor shell, and forming to obtain the lithium ion capacitor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119351052A (en) * | 2024-12-26 | 2025-01-24 | 锦州凯美电子科技有限公司 | A binder and its preparation method and application in lithium ion capacitor |
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| US20120321913A1 (en) * | 2010-02-26 | 2012-12-20 | Shanghai Aowei Technology Development Co., Ltd. | Manufacturing method for long-lived negative electrode and capacitor battery adopting the same |
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Application publication date: 20211102 |