CN113675008A - Polymer-based solid supercapacitor and preparation method and application thereof - Google Patents
Polymer-based solid supercapacitor and preparation method and application thereof Download PDFInfo
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- CN113675008A CN113675008A CN202110923659.4A CN202110923659A CN113675008A CN 113675008 A CN113675008 A CN 113675008A CN 202110923659 A CN202110923659 A CN 202110923659A CN 113675008 A CN113675008 A CN 113675008A
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- polyvinylidene fluoride
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- hexafluoropropylene
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 2
- 229910015866 LiNi0.8Co0.1Al0.1O2 Inorganic materials 0.000 claims description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 229910019240 Pr4NBF4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 23
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000011245 gel electrolyte Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
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- 238000010382 chemical cross-linking Methods 0.000 description 1
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- 229940034610 toothpaste Drugs 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a polymer-based solid supercapacitor and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a polyvinylidene fluoride-hexafluoropropylene copolymer and a solvent to obtain slurry; (2) coating the obtained slurry on a substrate, drying and stripping the substrate to obtain a polyvinylidene fluoride-hexafluoropropylene film; (3) preparing a battery core from the positive plate, the polyvinylidene fluoride-hexafluoropropylene film and the negative plate, connecting a tab, injecting electrolyte, and hot-pressing to obtain the polymer-based solid-state supercapacitor; according to the preparation method, the polyvinylidene fluoride-hexafluoropropylene copolymer film is used for replacing a traditional diaphragm to prepare the battery cell, and one step of hot pressing procedure is carried out after liquid injection, so that the interface contact performance of the battery cell is improved, and the finally obtained polymer-based solid super capacitor has high multiplying power and high power.
Description
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to a polymer-based solid supercapacitor and a preparation method and application thereof.
Background
The traditional super capacitor has the safety problems of electrolyte leakage, combustion explosion and the like, brings great potential safety hazards, cannot meet the application requirement of high safety, develops a solid/quasi-solid super capacitor, improves the safety of an energy storage device, and becomes the research focus of future energy storage equipment.
However, hydrogel electrolytes are mostly used in current solid/quasi-solid supercapacitors, and although the solid/quasi-solid supercapacitors have high conductivity and excellent rate and power, the working voltage and energy density are low, and the application development is limited. The organic all-solid-state electrolyte, the inorganic solid-state electrolyte and the organic gel electrolyte have wide potential windows and are suitable for high-energy solid/quasi-solid supercapacitors, but the organic all-solid-state electrolyte has low conductivity and is not suitable for being applied to high-power output supercapacitors. The inorganic solid electrolyte has problems of poor processability and poor interface contact with an electrode. The organogel electrolyte has an ionic conductivity of 10-4～10-2S/cm, and has excellent processability and film forming property, and is an ideal electrolyte for preparing solid capacitors.
CN105655149A discloses a flame-retardant fluorine-containing stretchable organogel electrolyte and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing a fluorine-containing rubber solution; (2) preparing a mixed solution of fluorine-containing rubber and organic polyamine containing active hydrogen; (3) preparing a fluororubber film; (4) preparing a fluororubber crosslinked film; (5) the prepared flame-retardant fluorine-containing stretchable organogel electrolyte has higher ionic conductivity, wider potential window and more excellent flame retardance and stretching resilience, and basically does not generate plastic deformation after the elongation is 100 percent and the cyclic stretching is carried out for 500 times; the method can be used for constructing a stretchable super capacitor with high energy density and high safety performance; the preparation method of the invention has simple process and is easy for industrial production. However, despite its high conductivity, the electrolyte is difficult to penetrate into the pore structure of the electrode sheet after chemical crosslinking, and the fluororubber has no polar functional group and has poor contact with the surface of the electrode sheet, so that the interfacial resistance of the solid supercapacitor constructed by the electrode sheet is large, and the rate and power characteristics of the cell are affected.
CN110600280A discloses a gel electrolyte precursor and its application in the preparation of low internal resistance quasi-solid super capacitor, the preparation of the low internal resistance quasi-solid super capacitor comprises the following steps: (1) assembling the positive pole piece, the negative pole piece and the isolating film into a bare cell, and then putting the bare cell into a shell to obtain a cell to be injected with liquid; (2) injecting the gel electrolyte precursor into the battery cell in vacuum, sealing, placing for 2-5 h, heating at 65-75 ℃ for 2-5 h, and initiating polymerization of the gel monomer; (3) and (4) forming a product, and performing performance test on the prepared low internal resistance standard solid-state supercapacitor. The low-internal-resistance quasi-solid super capacitor obtained by the invention has the characteristics of high conductivity, low internal resistance, ideal cycle and safety performance and the like. The method is simple in process and easy for large-scale production; however, the gel monomer is difficult to be uniformly polymerized, and the performance of the solid-state supercapacitor is affected.
Therefore, the development of a preparation method for preparing a polymer-based solid supercapacitor with high rate and high power is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polymer-based solid supercapacitor and a preparation method and application thereof; according to the preparation method, the polyvinylidene fluoride-hexafluoropropylene copolymer film is used for replacing a traditional diaphragm to prepare the battery cell, and after liquid injection, a hot pressing procedure is carried out for a plurality of steps, so that the gel part of the swollen polyvinylidene fluoride-hexafluoropropylene film permeates into the pore structure of the electrode plate, the interface contact performance of the battery cell is improved, and finally the polymer-based solid supercapacitor with high magnification and high power is successfully prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polymer-based solid supercapacitor, the method comprising the steps of:
(1) mixing a polyvinylidene fluoride-hexafluoropropylene copolymer and a solvent to obtain slurry;
(2) coating the slurry obtained in the step (1) on a substrate, drying and stripping the substrate to obtain a polyvinylidene fluoride-hexafluoropropylene film;
(3) and (3) preparing the positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the negative plate into a battery cell, connecting a tab, injecting electrolyte, and performing hot pressing to obtain the polymer-based solid supercapacitor.
The preparation method of the polymer-based solid supercapacitor provided by the invention comprises the steps of mixing a polyvinylidene fluoride-hexafluoropropylene copolymer and a solvent to obtain slurry; coating the slurry on a substrate, and peeling the substrate to successfully obtain a polyvinylidene fluoride-hexafluoropropylene film; replacing the traditional diaphragm with the polyvinylidene fluoride-hexafluoropropylene copolymer film, preparing a battery cell together with a positive plate and a negative plate, connecting a tab, injecting electrolyte, hot-pressing and the like, and successfully obtaining the polymer-based solid supercapacitor with high multiplying power and high power performance; the hot pressing process after the electrolyte is injected can effectively prevent the polyvinylidene fluoride-hexafluoropropylene membrane from wrinkling after absorbing the electrolyte and swelling to cause the problem of interface deterioration of the electrode plate and the electrolyte, the polyvinylidene fluoride-hexafluoropropylene membrane can be fully swelled by the high temperature of the hot pressing process to further form the gel electrolyte with high conductivity, and the high pressure of the hot pressing process can enable part of the swelled polyvinylidene fluoride-hexafluoropropylene gel electrolyte to penetrate into the pore structure of the electrode plate, so that the interface contact performance of the battery cell is improved, and the finally obtained polymer-based solid supercapacitor is favorably improved to have high multiplying power and high power performance.
The preparation method provided by the invention can be connected with the existing preparation process of the liquid super capacitor, is beneficial to the industrial production of the solid super capacitor, and has important research significance.
Preferably, the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer of step (1) is 3 × 105～10×105E.g. 4.5X 105、5×105、5.5×105、6×105、6.5×105、7×105、7.5×105、8×105、8.5×105、9×105Or 9.5X 105And the like.
Preferably, the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer of step (1) is 3-20%, for example, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, etc.
As a preferred technical scheme, the preparation method provided by the invention also controls the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer to be 3 x 105～10×105And the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer is 3-20%, so that the polyvinylidene fluoride-hexafluoropropylene copolymer has lower crystallinity and higher electrolyte swelling degree, can absorb a large amount of electrolyte, and further obtains high conductivity, thereby ensuring that the finally obtained polymer-based solid supercapacitor has high multiplying power and high power.
Preferably, the solvent of step (1) comprises N-methylpyrrolidone.
Preferably, the viscosity of the slurry of step (1) is 1000 to 10000 mPas, such as 2000 mPas, 3000 mPas, 4000 mPas, 5000 mPas, 6000 mPas, 7000 mPas, 8000 mPas or 9000 mPas.
Preferably, the drying temperature in step (2) is 70-110 ℃, such as 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or 105 ℃.
Preferably, the base body of step (2) comprises a current collector.
Preferably, the thickness of the polyvinylidene fluoride-hexafluoropropylene film in the step (2) is 15-50 μm, such as 15.5 μm, 16 μm, 16.5 μm, 17 μm, 17.5 μm, 18 μm, 18.5 μm, 19 μm or 19.5 μm.
Preferably, the active material in the positive electrode sheet in the step (3) comprises activated carbon and LiCoO2、LiMn2O4、LiNiO2、LiFePO4、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.8Co0.1Al0.1O2Any one or a combination of at least two of them.
Preferably, the active material in the negative electrode plate in the step (3) comprises any one of or a combination of at least two of active carbon, lithium titanate, hard carbon, soft carbon, graphite or mesocarbon microbeads.
In the present invention, the types of active materials in the positive electrode sheet and the negative electrode sheet are not particularly limited and may include, for example, the following combinations: a combination of positive activated carbon and negative activated carbon for the preparation of an electric double capacitor; a combination of positive active carbon and negative hard carbon for preparing a lithium ion capacitor; activated carbon and LiNi1/3Co1/3Mn1/3O2The mixture is used as the combination of the positive active material and the negative hard carbon for preparing the hybrid super capacitor, and the specific selection can be selected and matched according to the actual requirement.
Preferably, the battery core in the step (3) is manufactured by winding or laminating.
Preferably, step (3) further includes a step of side top sealing of the aluminum plastic film before injecting the electrolyte.
Preferably, the solute of the electrolyte in the step (3) comprises LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、LiAsF6、Et4BF4、Me3EtNBF4、Me2Et2NBF4、MeEt3NBF4、Et4NBF4、SBPBF4、Pr4NBF4Or MeBu3NBF4Any one or a combination of at least two of them.
Preferably, the solvent of the electrolyte in step (3) includes an ester solvent or a nitrile solvent.
Preferably, the ester-based solvent includes any one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, butylene carbonate, propyl methyl carbonate, ethyl acetate, or γ -butyrolactone, or a combination of at least two thereof.
Preferably, the nitrile solvent comprises any one or a combination of at least two of acetonitrile, propionitrile or butyronitrile.
Preferably, the solvent of the electrolyte in the step (3) is an ester solvent, and the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is preferably 5 to 20%, for example, 7%, 9%, 11%, 13%, 15%, 17%, 19%, or the like.
Preferably, the solvent of the electrolyte in the step (3) is a nitrile solvent, and the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is preferably 3 to 12%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or the like.
In the invention, the injection amount of the electrolyte in the step (3) is the sum of the pore volume of the positive plate, the pore volume of the negative plate and the volume of the polyvinylidene fluoride-hexafluoropropylene copolymer film which is 0.5 to 2.5 times (for example, 0.7 times, 0.9 times, 1.1 times, 1.3 times, 1.5 times, 1.7 times, 1.9 times, 2.1 times or 2.3 times and the like); the conductivity and strength of the polyvinylidene fluoride-hexafluoropropylene gel electrolyte are controlled by controlling the injection amount of the electrolyte.
Preferably, step (3) further comprises the steps of sealing and laying aside before the hot pressing.
As a preferred technical scheme of the invention, the step (3) of sealing and laying aside is further included before hot pressing, in the laying aside process, the polyvinylidene fluoride-hexafluoropropylene film initially forms gel electrolyte, and the hot pressing process can absorb more electrolyte and change the electrolyte into gel electrolyte with higher conductivity; it can be understood that: the polyvinylidene fluoride-hexafluoropropylene film and the electrolytic solution form a gel electrolyte by fusion, and at this time, the polyvinylidene fluoride-hexafluoropropylene copolymer has no "film" shape, similar to the state of toothpaste.
Preferably, the resting time is 2-48 h, such as 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h or 44 h.
Preferably, the pressure of the hot pressing in the step (3) is 0.05 to 3Mpa, such as 2Mpa, 4Mpa, 6Mpa, 8Mpa, 10Mpa, 12Mpa, 14Mpa, 16Mpa, 18Mpa, 20Mpa, 22Mpa, 24Mpa, 26Mpa or 28 Mpa.
Preferably, the hot pressing temperature in step (3) is 25-110 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the hot pressing time in the step (3) is 1-300 h, such as 10min, 50min, 70min, 90min, 120min, 150min, 180min, 210min, 250min or 280 min.
Preferably, after the hot pressing in the step (3) is finished, the method further comprises the steps of forming and secondary sealing.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing 3-20% of polyhexafluoroethylene by mass and 300000-1000000 of molecular weight of polyvinylidene fluoride-hexafluoropropylene copolymer with a solvent to obtain slurry with the viscosity of 1000-10000 mPa & s;
(2) coating the slurry obtained in the step (1) on a substrate, drying at 70-110 ℃, and stripping the substrate to obtain a polyvinylidene fluoride-hexafluoropropylene film with the thickness of 15-50 microns;
(3) and (3) winding or laminating the positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the negative plate to prepare a battery cell, connecting a tab, performing side top sealing on the aluminum plastic film, injecting electrolyte, sealing, standing for 2-48 h, performing hot pressing for 1-300 min at 0.05-3 Mpa and at 25-110 ℃, and performing formation and secondary sealing to obtain the polymer-based solid supercapacitor.
In a second aspect, the present invention provides a polymer-based solid-state supercapacitor prepared by the preparation method according to the first aspect.
In a third aspect, the invention provides a polymer-based solid-state supercapacitor according to the second aspect, and an application of the polymer-based solid-state supercapacitor in electronic products.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the polymer-based solid supercapacitor, the polyvinylidene fluoride-hexafluoropropylene copolymer film is used for replacing a traditional diaphragm to prepare the battery cell, and after liquid injection, a hot pressing procedure is carried out for a plurality of steps, so that the swollen polyvinylidene fluoride-hexafluoropropylene gel partially permeates into a pore structure of an electrode plate, the interface contact performance of the battery cell is improved, and finally the polymer-based solid supercapacitor with high multiplying power and high power is successfully prepared.
(2) The preparation method provided by the invention is similar to the existing preparation process of the liquid super capacitor, has simple process, can reduce equipment cost, and is beneficial to industrial production of the solid super capacitor.
(3) The preparation method provided by the invention is suitable for preparing electric double layer capacitors, lithium ion capacitors and hybrid capacitors, and has wide applicability.
(4) The preparation method provided by the invention takes the polyvinylidene fluoride-hexafluoropropylene copolymer as the gel electrolyte, has the advantages of high ionic conductivity and small interface resistance with an electrode, and further ensures that the prepared super capacitor has high multiplying power and power.
Drawings
FIG. 1 is a graph of multiplying power-capacitance of the polymer-based solid-state supercapacitor obtained in example 1;
fig. 2 is a time-voltage graph of the polymer-based solid-state supercapacitor obtained in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a polymer-based solid-state supercapacitor comprises the following steps:
(1) dissolving a polyvinylidene fluoride-hexafluoropropylene copolymer with the molecular weight of 50 ten thousand and the mass percentage content of polyhexafluoroethylene of 8 percent in N-methyl pyrrolidone, and mixing to obtain slurry with the viscosity of 3000mPa & s;
(2) coating the slurry obtained in the step (1) on a current collector, drying at 100 ℃, and stripping the current collector to obtain a polyvinylidene fluoride-hexafluoropropylene film with the thickness of 30 microns;
(3) laminating the activated carbon positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the activated carbon negative plate to prepare a battery core, drying at high temperature, ultrasonically welding a tab, sealing the top and the side of the aluminum-plastic film, and injecting 1M Et4BF4And (3) sealing the acetonitrile electrolyte (the electrolyte injection amount is the sum of the pore volume of the positive plate, the pore volume of the negative plate and the volume of the polyvinylidene fluoride-hexafluoropropylene film), standing for 24 hours, hot-pressing at 45 ℃ and 0.1Mpa for 10min, forming and secondary sealing to obtain the polymer-based solid supercapacitor.
Example 2
A preparation method of a polymer-based solid-state supercapacitor comprises the following steps:
(1) dissolving a polyvinylidene fluoride-hexafluoropropylene copolymer with the molecular weight of 45 ten thousand and the mass percentage content of polyhexafluoroethylene of 10 percent in N-methyl pyrrolidone, and mixing to obtain slurry with the viscosity of 3500mPa & s;
(2) coating the slurry obtained in the step (1) on a current collector, drying at 90 ℃, and stripping the current collector to obtain a polyvinylidene fluoride-hexafluoropropylene film with the thickness of 25 microns;
(3) laminating the activated carbon positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the hard carbon negative plate to prepare a battery core, drying the battery core at high temperature, ultrasonically welding a lug, sealing the top and the side of an aluminum-plastic film, and injecting 1M LiPF6And (3) sealing, standing for 20h, carrying out hot pressing for 2h at 55 ℃ and 0.2Mpa, forming and secondary sealing to obtain the polymer-based solid supercapacitor, wherein the electrolyte injection amount is the sum of the pore volume of the positive plate, the pore volume of the negative plate and the volume of the polyvinylidene fluoride-hexafluoropropylene film which is 0.8 times that of the positive plate, and the polymer-based solid supercapacitor is obtained.
Example 3
A preparation method of a polymer-based solid-state supercapacitor comprises the following steps:
(1) dissolving a polyvinylidene fluoride-hexafluoropropylene copolymer with the molecular weight of 55 ten thousand and the mass percentage content of polyhexafluoroethylene of 12 percent in N-methyl pyrrolidone, and mixing to obtain slurry with the viscosity of 4000mPa & s;
(2) coating the slurry obtained in the step (1) on a current collector, drying at 105 ℃, and stripping the current collector to obtain a polyvinylidene fluoride-hexafluoropropylene film with the thickness of 35 microns;
(3) mixing activated carbon and LiNi1/3Co1/3Mn1/3O2The composite positive plate (wherein the active carbon and LiNi in the composite positive plate)1/3Co1/3Mn1/3O2The mass ratio of the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) to the hard carbon negative plate is 3:7), the polyvinylidene fluoride-hexafluoropropylene film and the hard carbon negative plate are laminated to prepare a battery core, the battery core is dried at high temperature, a tab is welded by ultrasonic, the top and the side of an aluminum plastic film are sealed, and 1M LiPF is injected6And (3) sealing, standing for 30h, carrying out hot pressing at 65 ℃ and 0.1Mpa for 30min, forming and secondary sealing to obtain the polymer-based solid supercapacitor, wherein the electrolyte injection amount is the sum of the pore volume of the positive plate, the pore volume of the negative plate and the volume of the polyvinylidene fluoride-hexafluoropropylene film which is 0.6 times that of the positive plate, and the polymer-based solid supercapacitor is obtained.
Example 4
A method for manufacturing a polymer-based solid supercapacitor, which is different from example 1 only in that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is 30 ten thousand, the mass percentage of the polyvinylidene fluoride-hexafluoropropylene copolymer is 3%, and other components, conditions and steps are the same as those of example 1.
Example 5
A method for preparing a polymer-based solid supercapacitor, which is different from example 1 only in that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is 100 ten thousand, the mass percentage of the polyvinylidene fluoride-hexafluoropropylene copolymer is 12%, and other components, conditions and steps are the same as those of example 1.
Example 6
A method for manufacturing a polymer-based solid supercapacitor, which is different from example 1 only in that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is 20 ten thousand, the mass percentage of the polyvinylidene fluoride-hexafluoropropylene copolymer is 2%, and other components, conditions and steps are the same as those of example 1.
Example 7
A method for preparing a polymer-based solid supercapacitor, which is different from example 1 only in that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is 150 ten thousand, the mass percentage of the polyvinylidene fluoride-hexafluoropropylene copolymer is 25%, and other components, conditions and steps are the same as those of example 1.
Example 8
A method for preparing a polymer-based solid supercapacitor, which is different from example 2 only in that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer is 20 ten thousand, the mass percentage of the polyvinylidene fluoride-hexafluoropropylene copolymer is 2%, and other components, conditions and steps are the same as those of example 2.
Comparative example 1
A preparation method of a polymer-based solid-state supercapacitor comprises the following steps:
(1) dissolving a polyvinylidene fluoride homopolymer with the molecular weight of 50 ten thousand in N-methyl pyrrolidone, and mixing to obtain slurry with the viscosity of 3000mPa & s;
(2) coating the slurry obtained in the step (1) on a current collector, drying at 100 ℃, and stripping the current collector to obtain a polyvinylidene fluoride film with the thickness of 30 microns;
(3) laminating the activated carbon positive plate, the polyvinylidene fluoride film obtained in the step (2) and the activated carbon negative plate to prepare a battery cell, drying the battery cell at high temperature, ultrasonically welding a tab, sealing the top and the side of the aluminum-plastic film, and injecting 1M Et4BF4Sealing the acetonitrile electrolyte (the electrolyte injection amount is the sum of the pore volume of the positive plate, the pore volume of the negative plate and the volume of the polyvinylidene fluoride film), standing for 24h, hot-pressing at 45 ℃ and 0.1Mpa for 10min, forming and secondary sealing to obtain the polymer-based solid super capacitorA device.
Comparative example 2
The preparation method of the polymer-based solid supercapacitor is different from that of example 1 only in that a hot pressing step is not carried out, formation and secondary sealing are directly carried out to obtain the polymer-based solid supercapacitor, and other steps are the same as those of example 1.
And (3) performance testing:
(1) rate capability: the capacitance retention rate of the obtained polymer-based solid-state supercapacitor under different multiplying power conditions is tested by adopting an Arbin BT2000 charge-discharge test system, and the ratio of the capacitance under 200C or 20C discharge to the capacitance under 1C discharge is calculated.
The polymer-based solid supercapacitor obtained in example 1 is tested according to the test method, and the multiplying power-capacitance curve of the polymer-based solid supercapacitor obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the capacitance of the polymer-based solid supercapacitor obtained in example 1 at 200C discharge is 83.6% of the capacitance at 1C discharge.
(2) The charge and discharge performance is as follows:
the polymer-based solid supercapacitor obtained in example 1 is tested according to the 50C current charging and 50C current discharging test method, and the time-voltage curve graph of the polymer-based solid supercapacitor obtained in example 1 is shown in FIG. 2, and as can be seen from FIG. 2, the time-voltage curve graph of the polymer-based solid supercapacitor obtained in example 1 is close to an isosceles triangle, which shows that the voltage and the time have a good linear relationship, and the polymer-based solid supercapacitor has good capacitance characteristics.
The polymer-based solid-state supercapacitors obtained in examples 1 to 7 and comparative examples 1 to 3 were tested according to the test method described above, and the test results are shown in table 1:
TABLE 1
| Charge and discharge Properties (%) | |
| Example 1 | 83.6(200C) |
| Example 2 | 80.5(20C) |
| Example 3 | 73.1(20C) |
| Example 4 | 65.2(200C) |
| Example 5 | 84.1(200C) |
| Example 6 | 39.2(200C) |
| Example 7 | 82.6(200C) easy short-circuit |
| Example 8 | 38.8(20C) |
| Comparative example 1 | 11.2(200C) |
| Comparative example 2 | 22.9(200C) |
According to the data in table 1, the polymer-based solid supercapacitor provided by the invention has excellent charge and discharge performance, specifically, the capacitance of the supercapacitor obtained in examples 1 and 4 to 7 under 200C discharge is 39.2 to 84.1% of the capacitance under 1C discharge, and the capacitance of the supercapacitor obtained in examples 2 to 3 and 8 under 20C discharge is 38.8 to 80.5% of the capacitance under 1C discharge;
comparing example 1 with comparative example 1, it can be seen that the super capacitor obtained by replacing the polyvinylidene fluoride-hexafluoropropylene film with the polyvinylidene fluoride film has poor charge and discharge performance; as can be seen from comparison between example 1 and comparative example 2, the charging and discharging performance of the supercapacitor obtained without the hot pressing step is also poor, and it is proved that the supercapacitor with excellent charging and discharging performance can be obtained only by using the polyvinylidene fluoride-hexafluoropropylene film in combination with the hot pressing step.
Further comparing examples 1 and 4 to 7, and comparing examples 2 and 8, it can be seen that the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer was controlled to be 3X 105～10×105And the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer is 3-20%, so that the obtained capacitor has the best charge and discharge performance, and if the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer is too high, the performance is good, but the capacitor is easy to be short-circuited, and the charge and discharge performance cannot be tested.
The applicant states that the present invention is illustrated by the above examples to a polymer-based solid supercapacitor and its preparation method and application, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A preparation method of a polymer-based solid supercapacitor is characterized by comprising the following steps:
(1) mixing a polyvinylidene fluoride-hexafluoropropylene copolymer and a solvent to obtain slurry;
(2) coating the slurry obtained in the step (1) on a substrate, drying and stripping the substrate to obtain a polyvinylidene fluoride-hexafluoropropylene film;
(3) and (3) preparing the positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the negative plate into a battery cell, connecting a tab, injecting electrolyte, and performing hot pressing to obtain the polymer-based solid supercapacitor.
2. The production method according to claim 1, wherein the molecular weight of the polyvinylidene fluoride-hexafluoropropylene copolymer of step (1) is 30 to 100 ten thousand;
preferably, the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is 3-20%;
preferably, the solvent of step (1) comprises N-methylpyrrolidone;
preferably, the viscosity of the slurry in the step (1) is 1000-10000 mPa & s.
3. The method according to claim 1 or 2, wherein the drying temperature in step (2) is 70 to 110 ℃;
preferably, the substrate of step (2) comprises a current collector;
preferably, the thickness of the polyvinylidene fluoride-hexafluoropropylene film in the step (2) is 15-50 μm.
4. The production method according to any one of claims 1 to 3, wherein the active material in the positive electrode sheet of step (3) comprises activated carbon, LiCoO2、LiMn2O4、LiNiO2、LiFePO4、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.8Co0.1Al0.1O2Any one or a combination of at least two of;
preferably, the active material in the negative electrode plate in the step (3) comprises any one or a combination of at least two of active carbon, lithium titanate, hard carbon, soft carbon, graphite or mesocarbon microbeads;
preferably, the battery core in the step (3) is manufactured by winding or laminating.
5. The preparation method according to any one of claims 1 to 4, characterized in that the step (2) further comprises a step of side top sealing of an aluminum-plastic film before the electrolyte is injected;
preferably, the solute of the electrolyte in the step (3) comprises LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、LiAsF6、Et4BF4、Me3EtNBF4、Me2Et2NBF4、MeEt3NBF4、Et4NBF4、SBPBF4、Pr4NBF4Or MeBu3NBF4Any one or a combination of at least two of;
preferably, the solvent of the electrolyte in the step (3) comprises an ester solvent or a nitrile solvent;
preferably, the ester-based solvent includes any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, butylene carbonate, propyl methyl carbonate, ethyl acetate, or γ -butyrolactone;
preferably, the nitrile solvent comprises any one or a combination of at least two of acetonitrile, propionitrile, or butyronitrile;
preferably, the solvent of the electrolyte in the step (3) is an ester solvent, and the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is 5-20%;
preferably, the solvent of the electrolyte in the step (3) is a nitrile solvent, and the mass percentage of the polyhexafluoroethylene in the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is 3-12%;
preferably, the injection amount of the electrolyte in the step (3) is the sum of the pore volume of the positive plate, the pore volume of the negative plate and 0.5-2.5 times of the volume of the polyvinylidene fluoride-hexafluoropropylene copolymer film.
6. The method according to any one of claims 1 to 5, wherein the step (3) further comprises a step of sealing and laying aside before the hot pressing;
preferably, the time for the rest is 2-48 h.
7. The method according to any one of claims 1 to 6, wherein the pressure of the hot pressing in the step (3) is 0.05 to 3 MPa;
preferably, the temperature of the hot pressing in the step (3) is 25-110 ℃;
preferably, the hot pressing time in the step (3) is 1-300 min;
preferably, after the hot pressing in the step (3) is finished, the method further comprises the steps of forming and secondary sealing.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing 3-20% of polyhexafluoroethylene by mass and 30-100 ten thousand molecular weight polyvinylidene fluoride-hexafluoropropylene copolymer with a solvent to obtain slurry with the viscosity of 1000-10000 mPa & s;
(2) coating the slurry obtained in the step (1) on a substrate, drying at 70-110 ℃, and stripping the substrate to obtain a polyvinylidene fluoride-hexafluoropropylene film with the thickness of 15-50 microns;
(3) and (3) preparing the positive plate, the polyvinylidene fluoride-hexafluoropropylene film obtained in the step (2) and the negative plate into a battery cell by adopting a winding or laminating method, connecting a tab, performing side top sealing on the aluminum plastic film, injecting electrolyte, sealing, standing for 2-48 h, performing hot pressing for 1-300 min at 0.05-3 Mpa and at 25-110 ℃, forming and secondary sealing to obtain the polymer-based solid supercapacitor.
9. A polymer-based solid-state supercapacitor, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the polymer-based solid-state supercapacitor of claim 9 in an electronic product.
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| JP2003077539A (en) * | 2001-09-04 | 2003-03-14 | Mitsubishi Materials Corp | Gel polymer electrolyte and lithium polymer battery using the same |
| US20040146785A1 (en) * | 2000-03-17 | 2004-07-29 | Toru Mizutani | Gel electrolyte battery |
| CN103779089A (en) * | 2012-10-26 | 2014-05-07 | 海洋王照明科技股份有限公司 | Gel polymer dielectric and preparation method for the same, super capacitor and application thereof |
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| US20040146785A1 (en) * | 2000-03-17 | 2004-07-29 | Toru Mizutani | Gel electrolyte battery |
| JP2003077539A (en) * | 2001-09-04 | 2003-03-14 | Mitsubishi Materials Corp | Gel polymer electrolyte and lithium polymer battery using the same |
| CN103779089A (en) * | 2012-10-26 | 2014-05-07 | 海洋王照明科技股份有限公司 | Gel polymer dielectric and preparation method for the same, super capacitor and application thereof |
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