CN112490012A - Soft package type hybrid capacitor battery and preparation method thereof - Google Patents
Soft package type hybrid capacitor battery and preparation method thereof Download PDFInfo
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- CN112490012A CN112490012A CN202011347135.7A CN202011347135A CN112490012A CN 112490012 A CN112490012 A CN 112490012A CN 202011347135 A CN202011347135 A CN 202011347135A CN 112490012 A CN112490012 A CN 112490012A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
Abstract
The invention discloses a soft package type hybrid capacitor battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the positive pole piece comprises activated carbon, NCM523, an sp conductive agent, a carbon nano tube conductive agent, a binder and an aluminum foil current collector; the invention also discloses a preparation method of the hybrid capacitor battery, which comprises the steps of preparing the positive and negative pole pieces, forming a naked battery cell, packaging, drying and pre-lithiating the naked battery cell, pouring out a pre-lithiation solution after the pre-lithiation is finished, and injecting an electrolyte. The first efficiency of the soft package type hybrid capacitor battery prepared by the method is improved from 35% to 104%, and the discharge capacity, energy density and power density of the battery are also greatly improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical power supplies, relates to a soft package type hybrid capacitor battery, and further relates to a preparation method of the hybrid capacitor battery.
Background
The super capacitor has the advantages of high power density (quick charging and quick discharging), long cycle life, wide working temperature range, good safety performance, environmental friendliness and the like, but the lower energy density (less than 10Wh/kg) of the super capacitor seriously hinders the further application of the super capacitor in the fields of electric vehicles, smart power grids and the like. The lithium ion battery has high energy density (150-. However, the low power density and safety of the lithium ion battery cause the problem of battery safety, which also affects the wide-range application of the lithium ion battery in the fields of new energy vehicles, power grids and energy storage.
Based on the respective advantages and problems of the super capacitor and the lithium ion battery, the lithium ion capacitor (an electrochemical power supply composed of a capacitive anode and a battery-type cathode) is naturally generated under the circumstances, and the high power density, the long cycle life and the high energy density of the super capacitor are considered, so that the lithium ion capacitor rapidly receives common attention of people. Although the appearance of the lithium ion capacitor perfectly solves the problems of the super capacitor and the lithium ion battery, the lithium ion capacitor has relatively low energy density and first effect, and is subject to the following problems.
In order to improve the energy density of the lithium ion capacitor, the lithium ion capacitor using a composite positive electrode or a composite negative electrode is used (the lithium ion capacitor using the composite electrode is generally called as a hybrid capacitor battery in academia), but the problem of low first-pass efficiency of the hybrid capacitor battery is not solved.
There are many methods for improving the first effect of the hybrid capacitor battery, and the most important method is realized by a method of pre-lithiation of the negative electrode. Common negative electrode prelithiation methods include electrochemical methods, chemical methods and additive methods, and these methods are either complex in process and high in cost, or have poor compatibility with the current manufacturing process and cannot be applied in a large range, which also affects the large-scale application of lithium ion capacitors and hybrid capacitor batteries.
Disclosure of Invention
The invention aims to provide a soft package type hybrid capacitor battery.
The invention also aims to provide the preparation method of the hybrid capacitor battery, which has the characteristics of capability of greatly improving the first effect of the hybrid capacitor battery, simple pre-lithiation process and low cost.
The invention adopts the technical scheme that the soft package type hybrid capacitor battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises 65-70% of active carbon, 20-25% of NCM523, 2-5% of sp conductive agent, 1-3% of carbon nanotube conductive agent and 2-5% of adhesive by mass, wherein the sum of the contents of the active carbon, the NCM523, the sp conductive agent, the carbon nanotube conductive agent and the adhesive is 100%;
the negative pole piece comprises hard carbon, an sp conductive agent, a binder and a copper foil current collector, wherein the mass percentages of the hard carbon, the sp conductive agent and the binder are respectively 85-90%, 5-10% and 2-5%, and the sum of the contents of the raw materials is 100%;
the electrolyte includes lithium hexafluorophosphate, a solvent and an additive.
The invention is also characterized in that:
the solvent in the electrolyte is a mixture of two or more of EC, DEC and DMC; the additives in the electrolyte comprise an SEI film forming agent and a stabilizer.
The binder in the positive pole piece is any one or a mixture of more than two of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
The conductive agent in the positive pole piece is any one or a mixture of more than two of sp, carbon nano tube and graphene.
The diaphragm is a polypropylene basal membrane, the thickness of the diaphragm is 10um, and the surface density of the diaphragm is 12.65g/m2。
The invention adopts another technical scheme that the preparation method of the soft package type hybrid capacitor battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises 65-70% of active carbon, 20-25% of NCM523, 2-5% of sp conductive agent, 1-3% of carbon nanotube conductive agent and 2-5% of adhesive by mass, wherein the sum of the contents of the active carbon, the NCM523, the sp conductive agent, the carbon nanotube conductive agent and the adhesive is 100%;
the negative pole piece comprises hard carbon, an sp conductive agent, a binder and a copper foil current collector, wherein the mass percentages of the hard carbon, the sp conductive agent and the binder are respectively 85-90%, 5-10% and 2-5%, and the sum of the contents of the raw materials is 100%;
the electrolyte comprises lithium hexafluorophosphate, a solvent and an additive;
step 1, preparing a positive pole piece and a negative pole piece according to the composition of the positive pole piece and the negative pole piece;
step 2, using a polypropylene base film as a diaphragm, and manufacturing a positive pole piece and a negative pole piece into a bare cell in a laminated or winding manner;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the encapsulated bare cell obtained in the step 4 in a vacuum glove box for drying;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting the electrolyte from the liquid injection port, standing for 30-90min, and sealing to obtain the soft-package type hybrid capacitor battery.
The other technical scheme of the invention is also characterized in that:
in the step 1, the capacity ratio of the negative pole piece to the positive pole piece is 3.0-5.0.
The surface density of the positive pole piece in the step 1 is 320-360g/m2The surface density of the negative pole piece is 144-172g/m2。
In the step 5, the drying temperature is 60-120 ℃, and the drying time is 24-72 h.
In the step 6, the concentration of the glycol dimethyl ether solution of the diphenyl lithium is 0.1-1.0mol/L, and the prelithiation time is 10-600 s.
The invention has the beneficial effects that: according to the invention, the whole naked electric core is pre-lithiated, so that the operation process of pre-lithiation is reduced, and the problems of negative electrode oxidation and material falling caused by only pre-lithiation of the negative electrode and then drying of the negative electrode are avoided; the pre-lithiation degree of the soft package type hybrid capacitor battery, namely the pre-lithiation degree of the hard carbon cathode, is accurately controlled by adjusting the concentration of the pre-lithiation reagent and the pre-lithiation time, so that the first effect and the discharge capacity of the soft package type hybrid capacitor battery are greatly improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a soft package type hybrid capacitor battery, which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises active carbon and LiNi0.5Co0.2Mn0.3O2(NCM 523), sp conductive agent, carbon nano tube conductive agent, adhesive and aluminum foil current collector, wherein the mass percentages of the active carbon, the NCM523, the sp conductive agent, the carbon nano tube conductive agent and the adhesive are respectively 65-70%, 20-25%, 2-5%, 1-3% and 2-5%, and the sum of the contents of the above raw materials is 100%;
the negative pole piece comprises hard carbon, an sp conductive agent, a binder and a copper foil current collector, wherein the mass percentages of the hard carbon, the sp conductive agent and the binder are respectively 85-90%, 5-10% and 2-5%, and the sum of the contents of the raw materials is 100%;
the electrolyte comprises lithium hexafluorophosphate, a solvent and an additive, wherein the solvent is a mixture of two or more of EC, DEC and DMC, and the additive comprises an SEI film forming agent and a stabilizing agent;
the binder is any one or a mixture of more than two of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol;
the conductive agent in the positive pole piece is any one or a mixture of more than two of sp, a carbon nanotube and graphene;
the diaphragm is a polypropylene basal membrane, the thickness of the diaphragm is 10um, and the surface density of the diaphragm is 12.65g/m2；
The preparation method of the soft package type hybrid capacitor battery is implemented according to the following steps:
step 1, preparing a positive pole piece and a negative pole piece;
respectively weighing the following raw materials of the positive pole piece in percentage by mass:
65-70% of activated carbon, 52320-25% of NCM, 2-5% of sp conductive agent, 1-3% of carbon nano tube conductive agent and 2-5% of binder, wherein the total content of the raw materials is 100%;
weighing the following raw materials of the negative pole piece according to mass percentage:
85-90% of hard carbon, 5-10% of sp conductive agent and 2-5% of binder, wherein the sum of the contents of the raw materials is 100%;
mixing the weighed anode plate raw materials and cathode plate raw materials, and respectively and uniformly coating the mixture on 30um aluminum foil and 9um copper foil, wherein the capacity ratio of the cathode plate to the anode plate is 3.0-5.0, and the surface density of the anode plate is 320-360g/m2The surface density of the negative pole piece is 144-172g/m2Placing the positive pole piece and the negative pole piece in an oven for vacuum drying, and then punching the positive pole piece and the negative pole piece into required sizes by using a punching machine, wherein the size of the positive pole piece is 71mm (L) × 56mm (W), and the size of the negative pole piece is 75mm (L) × 60mm (W);
step 2, taking 15 positive pole pieces and 16 negative pole pieces, manufacturing a naked electric core in a laminated or winding mode, and using a polypropylene base film as a diaphragm;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film, a square aluminum shell or a cylindrical stainless steel shell with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the packaged bare cell obtained in the step 4 in a vacuum glove box for drying at the temperature of 60-120 ℃ for 24-72 hours, and then performing moisture detection, wherein the moisture of the positive and negative electrode plates is less than 300ppm, and the moisture of the diaphragm is less than 200ppm, so that the next step can be performed; otherwise, continuing baking until the moisture reaches the standard;
step 6, carrying out pre-lithiation on the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium, wherein the concentration of the ethylene glycol dimethyl ether solution of the diphenyl lithium is 0.1-1.0mol/L, and the pre-lithiation time is 10-600 s;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting the electrolyte from the liquid injection port, standing for 30-90min, and sealing to obtain the soft-package type hybrid capacitor battery.
Example 1
A preparation method of a soft package type hybrid capacitor battery is implemented according to the following steps:
step 1, preparing a positive pole piece and a negative pole piece;
respectively weighing the following raw materials of the positive pole piece in percentage by mass:
67.5% of activated carbon, 3% of NCM 52322.5%, 3% of sp conductive agent, 3% of carbon nanotube conductive agent and 4% of binder;
weighing the following raw materials of the negative pole piece according to mass percentage:
85% of hard carbon, 10% of sp conductive agent and 5% of binder;
mixing the weighed raw materials of the positive pole piece and the negative pole piece, and respectively and uniformly coating the mixture on an aluminum foil of 30um and a copper foil of 9um, wherein the capacity ratio of the negative pole piece to the positive pole piece is 3.0, and the surface density of the positive pole piece is 320g/m2The surface density of the negative pole piece is 152g/m2Placing the positive pole piece and the negative pole piece in an oven for vacuum drying, and then punching by using a punching machine to obtain: the size of the positive pole piece is 71mm (L) × 56mm (W), and the size of the negative pole piece is 75mm (L) × 60mm (W);
step 2, taking 15 positive pole pieces and 16 negative pole pieces, manufacturing a naked electric core in a laminated mode, and using a polypropylene base film as a diaphragm;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the packaged bare cell obtained in the step 4 in a vacuum glove box for drying at the drying temperature of 60 ℃ for 72 hours, and then performing moisture detection, wherein the moisture of the positive and negative electrode plates is less than 300ppm, and the moisture of the diaphragm is less than 200ppm, so that the next step can be performed; otherwise, continuing baking until the moisture reaches the standard;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
preparing a 0.7mol/L glycol dimethyl ether (DME) solution of diphenyl lithium with the concentration of 200 mL: weighing 21.59g of biphenyl reagent, performing vacuum drying treatment at 80 ℃, removing moisture, adding 200mL of DME solvent, stirring and dissolving to obtain a DME solution of biphenyl, wherein the solution is colorless, then weighing 0.97g of high-purity lithium sheet, cutting into small squares by using a ceramic scissors, adding the small squares into the biphenyl solution, accelerating the reaction speed of biphenyl and lithium blocks by using magnetic stirring, gradually changing the solution from colorless to light yellow, and changing the solution into dark green after the lithium blocks are completely dissolved, namely obtaining 0.7mol/L ethylene glycol dimethyl ether solution of diphenyl lithium;
then, in a glove box filled with argon, 100mL of 0.7mol/L glycol dimethyl ether solution of diphenyl lithium is added into a soft package type mixed capacitor battery, and the prelithiation time is 10 s;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting 15g of electrolyte from the liquid injection port, standing for 30min, and sealing to obtain the soft-package type mixed capacitor battery.
The soft package type hybrid capacitor battery is formed by using blue electricity charge and discharge test equipment, the charge and discharge current is 0.1C, and relevant test data are shown in table 1.
Example 2
A preparation method of a soft package type hybrid capacitor battery is implemented according to the following steps:
step 1, preparing a positive pole piece and a negative pole piece;
respectively weighing the following raw materials of the positive pole piece in percentage by mass:
67.5% of activated carbon, 3% of NCM 52322.5%, 3% of sp conductive agent, 3% of carbon nanotube conductive agent and 4% of binder;
weighing the following raw materials of the negative pole piece according to mass percentage:
85% of hard carbon, 10% of sp conductive agent and 5% of binder;
mixing the weighed raw materials of the positive pole piece and the negative pole piece, and respectively and uniformly coating the mixture on an aluminum foil of 30um and a copper foil of 9um, wherein the capacity ratio of the negative pole piece to the positive pole piece is 3.0, and the surface density of the positive pole piece is 340g/m2The surface density of the negative pole piece is 162g/m2Placing the positive pole piece and the negative pole piece in an oven for vacuum drying, and then punching by using a punching machine to obtain: the size of the positive pole piece is 71mm (L) × 56mm (W), and the size of the negative pole piece is 75mm (L) × 60mm (W);
step 2, taking 15 positive pole pieces and 16 negative pole pieces, manufacturing a naked electric core in a laminated mode, and using a polypropylene base film as a diaphragm;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the packaged bare cell obtained in the step 4 in a vacuum glove box for drying at the drying temperature of 60 ℃ for 72 hours, and then performing moisture detection, wherein the moisture of the positive and negative electrode plates is less than 300ppm, and the moisture of the diaphragm is less than 200ppm, so that the next step can be performed; otherwise, continuing baking until the moisture reaches the standard;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
preparing a 0.5mol/L glycol dimethyl ether (DME) solution of diphenyl lithium with the concentration of 200 mL: weighing 15.42g of biphenyl reagent, performing vacuum drying treatment at 80 ℃, removing moisture, adding 200mL of DME solvent, stirring and dissolving to obtain a DME solution of biphenyl, wherein the solution is colorless, then weighing 0.69g of high-purity lithium sheet, cutting into small squares by using a ceramic scissors, adding the small squares into the biphenyl solution, accelerating the reaction speed of biphenyl and lithium blocks by using magnetic stirring, gradually changing the solution from colorless to light yellow, and changing the solution into dark green after the lithium blocks are completely dissolved, namely obtaining 0.5mol/L ethylene glycol dimethyl ether solution of diphenyl lithium;
then, in a glove box filled with argon, 100mL of 0.5mol/L glycol dimethyl ether solution of diphenyl lithium is added into a soft package type mixed capacitor battery, and the prelithiation time is 30 s;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting 15g of electrolyte from the liquid injection port, standing for 30min, and sealing to obtain the soft-package type mixed capacitor battery.
The soft package type hybrid capacitor battery is formed by using blue electricity charge and discharge test equipment, the charge and discharge current is 0.1C, and relevant test data are shown in table 1.
Example 3
A preparation method of a soft package type hybrid capacitor battery is implemented according to the following steps:
step 1, preparing a positive pole piece and a negative pole piece;
respectively weighing the following raw materials of the positive pole piece in percentage by mass:
67.5% of activated carbon, 3% of NCM 52322.5%, 3% of sp conductive agent, 3% of carbon nanotube conductive agent and 4% of binder;
weighing the following raw materials of the negative pole piece according to mass percentage:
85% of hard carbon, 10% of sp conductive agent and 5% of binder;
mixing the weighed raw materials of the positive pole piece and the negative pole piece, and respectively and uniformly coating the mixture on an aluminum foil of 30um and a copper foil of 9um, wherein the capacity ratio of the negative pole piece to the positive pole piece is 3.0, and the surface density of the positive pole piece is 350g/m2The surface density of the negative pole piece is 167g/m2Placing the positive pole piece and the negative pole piece in an oven for vacuum drying, and then punching by using a punching machineComprises the following steps: the size of the positive pole piece is 71mm (L) × 56mm (W), and the size of the negative pole piece is 75mm (L) × 60mm (W);
step 2, taking 15 positive pole pieces and 16 negative pole pieces, manufacturing a naked electric core in a laminated mode, and using a polypropylene base film as a diaphragm;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the packaged bare cell obtained in the step 4 in a vacuum glove box for drying at the drying temperature of 60 ℃ for 72 hours, and then performing moisture detection, wherein the moisture of the positive and negative electrode plates is less than 300ppm, and the moisture of the diaphragm is less than 200ppm, so that the next step can be performed; otherwise, continuing baking until the moisture reaches the standard;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
preparing a 0.3mol/L glycol dimethyl ether (DME) solution of diphenyl lithium with the concentration of 200 mL: weighing 9.25g of biphenyl reagent, performing vacuum drying treatment at 80 ℃, removing moisture, adding 200mL of DME solvent, stirring and dissolving to obtain a DME solution of biphenyl, wherein the solution is colorless, then weighing 0.42g of high-purity lithium sheet, cutting into small squares by using a ceramic scissors, adding the small squares into the biphenyl solution, accelerating the reaction speed of biphenyl and lithium blocks by using magnetic stirring, gradually changing the solution from colorless to light yellow, and changing the solution into dark green after the lithium blocks are completely dissolved, namely obtaining 0.3mol/L ethylene glycol dimethyl ether solution of diphenyl lithium;
then, in a glove box filled with argon, 100mL of 0.3mol/L glycol dimethyl ether solution of diphenyl lithium is added into a soft package type mixed capacitor battery, and the prelithiation time is 120 s;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting 15g of electrolyte from the liquid injection port, standing for 30min, and sealing to obtain the soft-package type mixed capacitor battery.
The soft package type hybrid capacitor battery is formed by using blue electricity charge and discharge test equipment, the charge and discharge current is 0.1C, and relevant test data are shown in table 1.
Example 4
A preparation method of a soft package type hybrid capacitor battery is implemented according to the following steps:
step 1, preparing a positive pole piece and a negative pole piece;
respectively weighing the following raw materials of the positive pole piece in percentage by mass:
67.5% of activated carbon, 3% of NCM 52322.5%, 3% of sp conductive agent, 3% of carbon nanotube conductive agent and 4% of binder;
weighing the following raw materials of the negative pole piece according to mass percentage:
85% of hard carbon, 10% of sp conductive agent and 5% of binder;
mixing the weighed raw materials of the positive pole piece and the negative pole piece, and respectively and uniformly coating the mixture on an aluminum foil of 30um and a copper foil of 9um, wherein the capacity ratio of the negative pole piece to the positive pole piece is 3.0, and the surface density of the positive pole piece is 360g/m2The surface density of the negative pole piece is 170g/m2Placing the positive pole piece and the negative pole piece in an oven for vacuum drying, and then punching by using a punching machine to obtain: the size of the positive pole piece is 71mm (L) × 56mm (W), and the size of the negative pole piece is 75mm (L) × 60mm (W);
step 2, taking 15 positive pole pieces and 16 negative pole pieces, manufacturing a naked electric core in a laminated mode, and using a polypropylene base film as a diaphragm;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the packaged bare cell obtained in the step 4 in a vacuum glove box for drying at the drying temperature of 60 ℃ for 72 hours, and then performing moisture detection, wherein the moisture of the positive and negative electrode plates is less than 300ppm, and the moisture of the diaphragm is less than 200ppm, so that the next step can be performed; otherwise, continuing baking until the moisture reaches the standard;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
preparing a 0.1mol/L glycol dimethyl ether (DME) solution of diphenyl lithium with the concentration of 200 mL: weighing 3.08g of biphenyl reagent, performing vacuum drying treatment at 80 ℃, removing moisture, adding 200mL of DME solvent, stirring and dissolving to obtain a DME solution of biphenyl, wherein the solution is colorless, then weighing 0.14g of high-purity lithium sheet, cutting into small squares by using a ceramic scissors, adding the small squares into the biphenyl solution, accelerating the reaction speed of biphenyl and lithium blocks by using magnetic stirring, gradually changing the solution from colorless to light yellow, and changing the solution into dark green after the lithium blocks are completely dissolved, namely obtaining 0.1mol/L ethylene glycol dimethyl ether solution of diphenyl lithium;
then, in a glove box filled with argon, 100mL of 0.1mol/L glycol dimethyl ether solution of diphenyl lithium is added into a soft package type mixed capacitor battery, and the prelithiation time is 600 s;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting 15g of electrolyte from the liquid injection port, standing for 30min, and sealing to obtain the soft-package type mixed capacitor battery.
The soft package type hybrid capacitor battery is formed by using blue electricity charge and discharge test equipment, the charge and discharge current is 0.1C, and relevant test data are shown in table 1.
TABLE 1
It can be seen from table 1 that, in the soft-package capacitor battery prepared by the method of the present invention, the ethylene glycol-dimethyl ether solution of diphenyllithium is used as the prelithiation reagent of the hybrid capacitor battery, and the prelithiation parameters (reagent concentration and prelithiation time) are adjusted to greatly improve the first charge-discharge efficiency and the initial discharge capacity of the battery (the highest first charge-discharge efficiency reaches 104%), and simultaneously, the prelithiation process of the capacitor battery is greatly simplified. Meanwhile, the prelithiation in the method has certain universality, and can also be applied to lithium ion capacitors and high-energy-density silicon negative electrode batteries.
Claims (10)
1. A soft package type hybrid capacitor battery is characterized by comprising a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises 65-70% of active carbon, 20-25% of NCM523, 2-5% of sp conductive agent, 1-3% of carbon nanotube conductive agent and 2-5% of adhesive by mass, wherein the sum of the contents of the active carbon, the NCM523, the sp conductive agent, the carbon nanotube conductive agent and the adhesive is 100%;
the negative pole piece comprises hard carbon, an sp conductive agent, a binder and a copper foil current collector, wherein the mass percentages of the hard carbon, the sp conductive agent and the binder are respectively 85-90%, 5-10% and 2-5%, and the sum of the contents of the raw materials is 100%;
the electrolyte includes lithium hexafluorophosphate, a solvent and an additive.
2. The pouch type hybrid capacitor battery as set forth in claim 1, wherein the solvent in the electrolyte is a mixture of two or more of EC, DEC and DMC; the additives in the electrolyte comprise an SEI film forming agent and a stabilizer.
3. The soft-package type hybrid capacitor battery according to claim 1, wherein the binder in the positive electrode plate is one or a mixture of two or more of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
4. The soft-package type hybrid capacitor battery according to claim 1, wherein the conductive agent in the positive electrode plate is any one or a mixture of two or more of sp, carbon nanotube and graphene.
5. The soft-package type hybrid capacitor battery of claim 1, wherein the separator is a polypropylene-based film, the thickness of the separator is 10um, and the surface density of the separator is 12.65g/m2。
6. A preparation method of a soft package type hybrid capacitor battery is characterized in that the soft package type hybrid capacitor battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
the positive pole piece comprises 65-70% of active carbon, 20-25% of NCM523, 2-5% of sp conductive agent, 1-3% of carbon nanotube conductive agent and 2-5% of adhesive by mass, wherein the sum of the contents of the active carbon, the NCM523, the sp conductive agent, the carbon nanotube conductive agent and the adhesive is 100%;
the negative pole piece comprises hard carbon, an sp conductive agent, a binder and a copper foil current collector, wherein the mass percentages of the hard carbon, the sp conductive agent and the binder are respectively 85-90%, 5-10% and 2-5%, and the sum of the contents of the raw materials is 100%;
the electrolyte comprises lithium hexafluorophosphate, a solvent and an additive;
step 1, preparing a positive pole piece and a negative pole piece according to the composition of the positive pole piece and the negative pole piece;
step 2, using a polypropylene base film as a diaphragm, and manufacturing a positive pole piece and a negative pole piece into a bare cell in a laminated or winding manner;
step 3, welding an aluminum tab for the positive pole piece in an ultrasonic welding mode, and welding a copper nickel-plated tab for the negative pole piece;
step 4, packaging the naked electric core processed in the step 3 by using an aluminum plastic film with the thickness of 110um, the width of 120mm and the length of 200mm, and reserving an air bag and a liquid injection port on the right side of the naked electric core;
step 5, placing the encapsulated bare cell obtained in the step 4 in a vacuum glove box for drying;
step 6, pre-lithiating the positive pole piece and the negative pole piece of the bare cell processed in the step 5 by using an ethylene glycol dimethyl ether solution of diphenyl lithium;
and 7, pouring out the ethylene glycol dimethyl ether solution of the diphenyl lithium after the pre-lithiation is finished, injecting the electrolyte from the liquid injection port, standing for 30-90min, and sealing to obtain the soft-package type hybrid capacitor battery.
7. The method for preparing the soft-package type hybrid capacitor battery according to claim 6, wherein the capacity ratio of the negative electrode plate to the positive electrode plate in the step 1 is 3.0-5.0.
8. The method as claimed in claim 6, wherein the surface density of the positive electrode plate in step 1 is 320-360g/m2The surface density of the negative pole piece is 144-172g/m2。
9. The method for preparing the soft-package type hybrid capacitor battery according to claim 6, wherein the drying temperature in the step 5 is 60-120 ℃ and the drying time is 24-72 h.
10. The method for preparing the soft package type hybrid capacitor battery according to claim 6, wherein the concentration of the glycol dimethyl ether solution of the diphenyl lithium in the step 6 is 0.1-1.0mol/L, and the prelithiation time is 10-600 s.
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| CN113078367A (en) * | 2021-03-29 | 2021-07-06 | 中南大学 | Manufacturing method of high-energy-density flexible package lithium ion battery |
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