CN114808521A - Method for preparing electrode precursor by using copper-plated carbon fiber papermaking - Google Patents
Method for preparing electrode precursor by using copper-plated carbon fiber papermaking Download PDFInfo
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- CN114808521A CN114808521A CN202210419300.8A CN202210419300A CN114808521A CN 114808521 A CN114808521 A CN 114808521A CN 202210419300 A CN202210419300 A CN 202210419300A CN 114808521 A CN114808521 A CN 114808521A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 221
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 221
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000002243 precursor Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007790 solid phase Substances 0.000 claims abstract description 29
- 238000005520 cutting process Methods 0.000 claims abstract description 26
- 238000007747 plating Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- 238000009713 electroplating Methods 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 239000000835 fiber Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 29
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- 239000002002 slurry Substances 0.000 claims description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 8
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 8
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 8
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 230000001235 sensitizing effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
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- 238000002791 soaking Methods 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000013055 pulp slurry Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
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- 238000007731 hot pressing Methods 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 229940117975 chromium trioxide Drugs 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- 229920000168 Microcrystalline cellulose Polymers 0.000 description 3
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- 238000007598 dipping method Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 235000019813 microcrystalline cellulose Nutrition 0.000 description 3
- 239000008108 microcrystalline cellulose Substances 0.000 description 3
- 229940016286 microcrystalline cellulose Drugs 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- VYZAMTAEIAYCRO-YPZZEJLDSA-N chromium-50 Chemical compound [50Cr] VYZAMTAEIAYCRO-YPZZEJLDSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
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Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Paper (AREA)
Abstract
The invention discloses a method for preparing an electrode precursor by using copper-plated carbon fiber papermaking, belonging to the field of conductive functional materials. The preparation method comprises the following steps: and carrying out pretreatment, electro-coppering treatment, cutting, wet papermaking and solid-phase sintering treatment on the continuous carbon fiber filaments to obtain the carbon fiber paper-based high-performance electrode precursor. The method adopts the method of copper plating and solid phase sintering, and the pulp is carbonized into carbon fibers in the solid phase sintering process, so that the interference of the pulp on the electrode preparation process and the influence on the electrode performance are eliminated; meanwhile, copper plating is heated and melted, so that the contact resistance is reduced, the carbon fibers are uniformly distributed to form bonding force, and the mechanical property required by the electrode precursor is ensured. The invention simplifies the preparation process of the electrode precursor, and the prepared electrode precursor has the characteristics of low cost, low resistivity, high thermal conductivity, good conduction stability and the like, and is a high-quality material for manufacturing high-performance capacitors.
Description
Technical Field
The invention belongs to the field of conductive functional materials, and particularly relates to a method for preparing an electrode precursor by using copper-plated carbon fiber papermaking.
Background
Carbon fiber is a special fiber composed of carbon elements, and gradually becomes a preferred material in national defense military industry, aerospace industry and high-grade civil product industry due to the characteristics of light weight, corrosion resistance, high temperature resistance, friction resistance, electric conduction, heat conduction, high strength, high modulus and the like. The carbon fiber paper is prepared by using chopped carbon fibers and pulp as raw materials through wet papermaking technology, resin impregnation, hot pressing, carbonization and other process flows, and has the characteristics of light weight, porosity, high conductivity, corrosion resistance, high temperature resistance and the like. The application of carbon fiber paper to capacitor electrodes has been the focus of recent research.
When the existing method is used for manufacturing the carbon fiber paper, in order to enhance the mechanical property of the carbon fiber paper precursor in the paper making process, the carbon fiber and the pulp are generally required to be matched and made, and in order to avoid the interference of the pulp on the electrode preparation process and the negative influence on the electrode property, the carbon fiber paper precursor is generally subjected to resin impregnation, hot pressing and carbonization to prepare the carbon fiber paper. The process of making carbon fiber paper by the existing method is not only complex, but also needs a complex resin modification process, and a complex carbonization process is needed after the resin modification.
The electrode precursor is prepared by the existing method, namely the carbon fiber paper is pretreated and electroplated with copper. When the carbon fiber paper is pretreated, the treatment process is difficult to control: too light treatment can lead to weak copper plating and poor conductivity of the electrode precursor; too heavy treatment can cause resin to fall off, and the mechanical property of the electrode precursor is poor. The electrode precursor prepared by the existing method consists of carbon fibers, dendritic carbides and a copper plating layer, and has a plurality of defects: the three have larger contact resistance, thus reducing the conductivity of the electrode; the thermal conductivity of the three materials is different, so that the thermal conductivity of the electrode is poor; the thermal expansion coefficients of the three components are different, so that the conduction stability of the electrode is poor.
Disclosure of Invention
The technical problem is as follows: the invention provides the preparation method of the high-performance electrode precursor, which is low in cost, low in resistivity, good in thermal conductivity, good in conductive stability, high-temperature resistance and good in heating stability, combines the processes of copper electroplating, wet papermaking, solid phase sintering and the like, is relatively simple to operate, is easy to realize, remarkably improves the performance of the electrode, and is suitable for large-scale production, and the problems of complex process, difficult process control, poor product performance and the like of the traditional electrode precursor preparation method are solved.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme.
The invention provides a method for preparing a high-performance electrode precursor by using copper-plated carbon fiber papermaking, which comprises the following steps:
(1) pretreatment: sequentially carrying out desizing treatment, coarsening treatment, neutralizing treatment, sensitizing treatment, activating treatment and reducing treatment on the carbon fiber filaments, washing with deionized water and drying;
(2) copper electroplating: placing the carbon fiber filament pretreated in the step (1) in an electroplating copper solution for electroplating, washing with deionized water after electroplating, and drying to obtain a copper-plated carbon fiber filament;
(3) cutting short: cutting the copper-plated carbon fiber filaments obtained in the step (2) into copper-plated chopped carbon fibers by a fiber cutting machine;
(4) wet papermaking: adding the copper-plated chopped carbon fibers obtained in the step (3) and the pulp subjected to defibering treatment into deionized water, and stirring to prepare slurry; then adding a dispersant, and mixing uniformly to prepare a papermaking suspension; then, screening and papermaking are carried out to obtain wet paper, and the wet paper is placed in a paper pattern presser for pressing and drying to obtain copper-plated carbon fiber paper;
(5) solid-phase sintering: and (5) treating the copper-plated carbon fiber paper obtained in the step (4) in an inert atmosphere by adopting a solid-phase sintering method to obtain an electrode precursor.
In one embodiment of the present invention, the carbon fiber filament in step (1) is a 12K carbon fiber filament bundle with a cross-sectional diameter of 5-9 um.
In one embodiment of the present invention, the drying conditions in step (1) are as follows: drying in an oven at 60-80 deg.C for 1-2 h.
In one embodiment of the present invention, the desizing treatment in step (1) is to soak carbon fiber filaments in acetone at room temperature for 10-20min, heat the acetone to 110-. The carbon fiber which is not subjected to desizing treatment (dipping and extraction) has black color band gloss on the surface, and the tows are stiff and flaky, so that the next processing of the fiber is not facilitated; the reason is that commercial carbon fibers are generally glued on the surfaces of the carbon fibers, and the surface gluing is to protect the carbon fibers in the operation processes of winding, weaving and the like, and is beneficial to further modifying the surfaces of the carbon fibers and improving the interlaminar shear strength of the carbon fiber composite material; however, the conductivity and hydrophilicity of carbon fiber are affected by surface sizing, and the conductivity, wettability and metal adhesion required by copper plating of carbon fiber are difficult to meet, so that the carbon fiber surface needs to be subjected to dipping extraction degumming treatment when the carbon fiber is applied. The acetone and the ethanol can not only reduce the surface energy of the carbon fiber, but also improve the wettability of the carbon fiber, and are good solvents; the surface of the carbon fiber subjected to desizing treatment loses luster and becomes soft tows, so that the subsequent treatment is facilitated.
In one embodiment of the present invention, the roughening treatment in step (1) is carried out by immersing carbon fiber filaments after desizing treatment in a roughening solution containing 50-150g/L chromium trioxide and 50-150g/L sulfuric acid for 5-20min, taking out, and washing with deionized water. The roughening aims to etch the surface of the carbon fiber by using the roughening solution to roughen the surface of the carbon fiber, so that the carbon fiber is favorably combined with the metal copper.
In one embodiment of the invention, the neutralization treatment in step (1) is to soak the coarsened carbon fiber filaments in 6-10g/L sodium hydroxide solution for 3-7min, and then take out and wash with deionized water.
In one embodiment of the invention, the sensitization treatment in the step (1) is to soak the neutralized carbon fiber filaments in a sensitization solution containing 0.1-0.2g/L hydrochloric acid and 35-45g/L stannous chloride for 15-25 min.
In one embodiment of the present invention, the activation treatment in step (1) is to take out the carbon fiber filaments after the sensitization treatment is finished, and soak the carbon fiber filaments in 0.3-0.7g/L of palladium chloride activation solution for 4-8 min.
In one embodiment of the invention, the reduction treatment in the step (1) is to take out the carbon fiber filaments after the activation treatment is finished, and soak the carbon fiber filaments in 25-35g/L sodium hypophosphite for 20-60 s.
In one embodiment of the present invention, the electrolytic copper plating solution in step (2) contains CuSO 4 ·5H 2 10-30g/L of O, 10-20g/L of sodium potassium tartrate, 10-30g/L of disodium ethylenediamine tetraacetic acid and 3-7mL/L of formaldehyde, wherein the electroplating voltage is 1-3V, the electroplating temperature is 40-60 ℃, and the electroplating time is more than 20 min.
In one embodiment of the present invention, the drying conditions in step (2) are: drying in an oven at 80 ℃ for 4-6 h.
In one embodiment of the invention, the copper-plated carbon fiber filament is cut into copper-plated chopped carbon fibers by a fiber cutting machine in the step (3), and the length of the copper-plated chopped carbon fibers is 2-8 mm.
In an embodiment of the present invention, the pulp in step (4) is one or more of natural plant fiber pulp, viscose fiber pulp, nano cellulose pulp, and microcrystalline cellulose pulp.
In an embodiment of the present invention, the defibering treatment in the step (4) is to weigh a certain amount of pulp into 1-2L of water, and defiber the pulp for 5-15min by using a fiber defibering device at a rotating speed of 3000 rpm. The purpose of defibering is to disperse the pulp uniformly.
The method for preparing the high-performance electrode precursor by using the copper-plated carbon fiber papermaking is characterized in that the slurry in the step (4) is prepared by using the copper-plated chopped carbon fibers and defibering pulp in an absolute dry mass ratio of (1-4): (6-9). The purpose of adding the pulp is to facilitate the paper sheet forming, the pulp is combined with each other, the mechanical property of the wet paper is improved, and the subsequent processing is facilitated.
In one embodiment of the present invention, the stirring speed in step (4) is 200-600rpm, and the stirring time is 1-10 min. The purpose of stirring is to mix the copper-plated chopped carbon fibers and the pulp uniformly.
In one embodiment of the present invention, the dispersant in step (4) is PEO and PAM; wherein, the adding amount of PEO is 0.1-0.5% of the weight of the oven dry slurry; the amount of PAM added is 0.05-0.2% of the weight of the oven dried pulp.
In one embodiment of the present invention, the pressing pressure in the step (4) is 10 to 60 MPa.
In one embodiment of the present invention, the drying in step (4) is drying by using a flat plate dryer.
In one embodiment of the present invention, the drying temperature in step (4) is 105-140 ℃, and the drying time is 5-20 min.
In one embodiment of the present invention, the sieving in the step (4) is performed by using an 80-mesh stainless steel sieve.
In one embodiment of the present invention, the solid phase sintering temperature in step (5) is 700-. The sintering has two purposes, one is to carbonize the pulp into conductive carbon fiber, so as to eliminate the interference of the pulp on the next electrode preparation process and the negative influence on the electrode performance; and secondly, the copper plating is heated and melted to form sintering joint points among the carbon fibers, so that new bonding force is formed among the carbon fibers, and the mechanical property required by the electrode precursor is ensured.
In one embodiment of the present invention, the inert atmosphere of step (5) comprises nitrogen.
The invention also provides an electrode precursor based on the method.
The invention also provides the application of the electrode precursor in the aspect of preparing a capacitor.
The invention has the beneficial effects that:
1. the invention prepares the high-performance electrode precursor by sequentially carrying out pretreatment, copper plating, cutting, wet paper making and solid-phase sintering on the carbon fiber, saves the processes of resin impregnation and hot pressing, does not need a complex resin modification process, avoids the negative influence on the electrode caused by the instability of the performance of the resin carbide on the carbon fiber paper, simplifies the preparation process of the electrode precursor, saves resources and reduces the cost.
2. The method of copper plating after carbon fiber pretreatment and solid phase sintering is adopted, so that the bonding firmness of copper and carbon fiber is high, the contact resistance is small, the prepared electrode precursor has low resistivity and good conductivity by combining the characteristics of good conductivity and low resistivity of metal copper.
3. The invention adopts the method of plating copper and then making paper, the copper is uniformly distributed among the carbon fiber, and the prepared electrode precursor has uniform and stable mechanical property, conductivity and heat conductivity.
4. The method adopts the solid phase sintering method in the nitrogen atmosphere, and the pulp is carbonized into carbon fibers in the solid phase sintering process, so that the interference of the pulp on the electrode preparation process and the negative influence on the electrode performance are eliminated; meanwhile, copper plating on the paper is heated and melted and is adhered to each other to form sintering joint points among the carbon fibers, so that new adhesion force is formed among the carbon fibers, and the mechanical property required by the electrode precursor is ensured.
5. The method is relatively simple to operate, easy to realize, beneficial to popularization and suitable for large-scale production.
6. The electrode precursor prepared by the invention has the characteristics of low cost, low resistivity, good thermal conductivity, good conductive stability, high temperature resistance, good heating stability and the like, and is a high-quality material for manufacturing high-performance capacitors.
Drawings
FIG. 1 is a schematic structural view of the copper-coated carbon fiber filament produced in example 1 of the present invention; wherein, 1-carbon fiber filament; 2-copper plating on the surface of the carbon fiber filament.
FIG. 2 is a schematic structural view of the copper-coated carbon fiber paper produced in example 1 of the present invention; wherein, 3-copper plating chopped carbon fiber; 4-pulp; 5-copper-plated carbon fiber paper.
FIG. 3 is a schematic structural diagram of the high performance electrode precursor prepared in example 1 of the present invention; wherein, the 6-copper plating chopped carbon fiber; 7-sintering the bonding points; 8-carbon fiber after pulp carbonization; 9-electrode precursor.
Detailed Description
The purpose of the invention is realized by the following technical scheme. The invention provides a method for preparing a high-performance electrode precursor by using copper-plated carbon fiber papermaking, which comprises the following steps:
(1) pretreatment: sequentially carrying out desizing treatment, coarsening treatment, neutralizing treatment, sensitizing treatment, activating treatment and reducing treatment on the carbon fiber filaments, washing with deionized water, and drying in an oven at 60-80 ℃ for 1-2 h;
(2) copper electroplating: placing the carbon fiber filament obtained in the step (1) in an electroplating copper solution for electroplating, washing with deionized water after electroplating, and drying in an oven at 80 ℃ for 4-6 h;
(3) cutting short: cutting the copper-plated carbon fiber filaments obtained in the step (2) into copper-plated chopped carbon fibers by a fiber cutting machine;
(4) wet papermaking: adding the copper-plated chopped carbon fibers obtained in the step (3) and the pulp subjected to defibering treatment into deionized water to prepare slurry, stirring, adding a dispersing agent, uniformly mixing to prepare a papermaking suspension, papermaking into wet paper through a 80-mesh stainless steel filter screen, placing the wet paper into a paper pattern presser for pressing, and drying by using a flat plate dryer to prepare copper-plated carbon fiber paper;
(5) solid-phase sintering: and (5) treating the copper-plated carbon fiber paper obtained in the step (4) in a nitrogen atmosphere by adopting a solid-phase sintering method to obtain the high-performance electrode precursor.
Further, the carbon fiber filament in the step (1) is a 12K carbon fiber filament bundle with the cross section diameter of 5-9 um.
Further, the desizing treatment in the step (1) is to soak the carbon fiber filaments in acetone at normal temperature for 10-20min, heat the acetone to 110-.
Furthermore, the coarsening treatment in the step (1) is that the carbon fiber filaments after the desizing treatment are soaked for 5-20min by coarsening liquid containing 50-150g/L of chromium trioxide and 50-150g/L of sulfuric acid, and the carbon fiber filaments are washed by deionized water after being taken out.
Further, step (ii)(2) The copper electroplating solution contains CuSO 4 ·5H 2 10-30g/L of O, 10-20g/L of sodium potassium tartrate, 10-30g/L of disodium ethylenediamine tetraacetic acid and 3-7mL/L of formaldehyde, wherein the electroplating voltage is 1-3V, the electroplating temperature is 40-60 ℃, and the electroplating time is more than 20 min.
Further, the method is characterized in that the copper-plated carbon fiber filaments are cut into copper-plated chopped carbon fibers by a fiber cutting machine in the step (3), and the length of the copper-plated chopped carbon fibers is 2-8 mm.
Further, the pulp in the step (4) is one or more of natural plant fiber, viscose fiber, nano-cellulose and microcrystalline cellulose.
Further, the defibering treatment in the step (4) is to weigh a certain amount of pulp and put the pulp into 1-2L of water, and defiber the pulp for 5-15min at the rotating speed of 3000rpm by a fiber defibering device.
Further, the slurry in the step (4) is prepared by mixing copper-plated chopped carbon fibers with defibered pulp in an oven-dry mass ratio of (1-4): (6-9).
Further, the stirring speed in the step (4) is 200-600rpm, and the stirring time is 1-10 min.
Further, the dispersant in the step (4) is PEO and PAM, the addition amount of PEO is 0.1-0.5% of the weight of the oven dry slurry, and the addition amount of PAM is 0.05-0.2% of the weight of the oven dry slurry.
Further, the pressing pressure in the step (4) is 10-60 MPa.
Further, the drying temperature in the step (4) is 105-.
Further, the solid phase sintering temperature in the step (5) is 700-1050 ℃, and the sintering time is 20-90 min.
The invention relates to reagents involved in the following implementation processes: the plant fiber pulp is Fengbao needle-leaf bleached kraft pulp (Fengbao NBKP) provided by the Jindong paper industry, and the batch number is 11163. Viscose pulp is manufactured by reference to the existing literature, the world of fibers (university press, Anhui). The nano-cellulose pulp is nano-cellulose hydrogel (TOCNF) provided by pulp and paper making research laboratory of Tianjin science and technology university, and can be purchased from Liquid Biotechnology Limited. The microcrystalline cellulose pulp was purchased from pharmaceutic adjuvant, Inc. of mountain river, Anhui, under a batch number of 190702. Carbon fiber filaments were purchased from Dongli carbon fiber (Guangdong) GmbH under a batch number of 20210716.
The present invention is further illustrated by the following examples.
Example 1
The embodiment comprises the following steps:
(1) pretreatment: soaking carbon fiber filaments with the diameter of 6 microns in acetone at normal temperature for 15min, heating the acetone to 120 ℃, performing reflux treatment in the acetone at the temperature of 120 ℃ for 10h, taking out the carbon fiber filaments, washing the carbon fiber filaments with the acetone for 2 times, soaking the carbon fiber filaments in absolute ethyl alcohol for 15min, taking out the carbon fiber filaments and washing the carbon fiber filaments with deionized water; soaking the treated carbon fiber filaments in a roughening solution containing 100g/L of chromium trioxide and 100g/L of sulfuric acid for 8min, taking out the carbon fiber filaments to be washed by deionized water, soaking the carbon fiber filaments in a sodium hydroxide solution of 8g/L for 5min, taking out the carbon fiber filaments to be washed by the deionized water, soaking the carbon fiber filaments in a sensitizing solution containing 0.15g/L of hydrochloric acid and 40g/L of stannous chloride for 20min, taking out the carbon fiber filaments to be soaked in an activating solution of 0.5g/L of palladium chloride for 6min, taking out the carbon fiber filaments to be soaked in 30g/L of sodium hypophosphite for 40s, washing the carbon fiber filaments by the deionized water, and drying the carbon fiber filaments in an oven at 70 ℃ for 1.5 h.
(2) Copper electroplating: putting the pretreated carbon fiber filament into a reactor containing CuSO 4 ·5H 2 Electroplating in an electroplating solution containing 20g/L of O, 15g/L of sodium potassium tartrate, 20g/L of disodium ethylene diamine tetraacetate and 4.1g/L of formaldehyde at the electroplating voltage of 2V and the electroplating temperature of 50 ℃ for 80min to obtain the copper-plated carbon fiber filament with the structure shown in figure 1.
(3) Cutting into short pieces: and cutting the copper-plated carbon fiber filaments into copper-plated short carbon fibers with the length of 6mm by a fiber cutting machine.
(4) Wet papermaking: weighing 0.51g (absolute dry mass) of plant fiber pulp, putting the plant fiber pulp into 2L of deionized water, defibering the plant fiber pulp by using a defibering device at the rotating speed of 3000rpm for 10min to prepare pulp slurry, weighing 2.00g (absolute dry mass) of the copper-plated chopped carbon fibers obtained in the step (3), putting the copper-plated chopped carbon fibers into the pulp slurry, adding 1L of deionized water, stirring the mixture at the rotating speed of 300rpm for 3min, adding 16mL of 0.05 wt% of PEO dispersant, adding the PEO dispersant into the mixture, and stirring the mixture4.8mL of 0.05 wt% PAM dispersant, stirring for 2min by a glass rod, mixing uniformly to prepare a papermaking suspension, transferring to a papermaking device, adding 3L of deionized water, stirring uniformly, papermaking into wet paper by a stainless steel filter screen of 80 meshes, putting the wet paper into a paper sample presser, pressing under 40MPa, and drying for 10min at 105 ℃ by a flat plate dryer to obtain the copper-plated carbon fiber paper, wherein the quantitative amount of the copper-plated carbon fiber paper is about 80g/m 2 . The structure of the copper-coated carbon fiber paper is shown in fig. 2.
(5) Solid-phase sintering: and (3) putting the copper-plated carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid-phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 30min, so that the high-performance electrode precursor can be obtained, and the structure of the high-performance electrode precursor is shown in figure 3.
Example 2
The embodiment comprises the following steps:
(1) and (4) preprocessing. The same as in example 1.
(2) Copper electroplating: putting the pretreated carbon fiber filament into a reactor containing CuSO 4 ·5H 2 Electroplating in an electroplating solution containing 20g/L of O, 15g/L of sodium potassium tartrate, 20g/L of disodium ethylene diamine tetraacetate and 4.1g/L of formaldehyde at the electroplating voltage of 2V and the electroplating temperature of 50 ℃ for 90min to obtain the copper-plated carbon fiber filament, wherein the structure of the copper-plated carbon fiber filament can be shown in figure 1.
(3) And (5) cutting short. The same as in example 1.
(4) Wet papermaking: weighing 0.63g (absolute dry mass) of plant fiber pulp, putting the plant fiber pulp into 2L of deionized water, defibering the pulp for 10min at the rotating speed of 3000rpm by using a defibering device to prepare pulp slurry, then weighing 2.51g (absolute dry mass) of the copper-plated chopped carbon fibers obtained in the step (3), putting the copper-plated chopped carbon fibers into the pulp slurry, adding 1L of deionized water, stirring the mixture for 3min at the rotating speed of 300rpm, adding 20mL of 0.05 wt% of PEO dispersant, adding 6mL of 0.05 wt% of PAM dispersant, stirring the mixture for 2min by using a glass rod, uniformly mixing the mixture to prepare paper-making suspension, transferring the paper-making suspension to a sheet-making machine, adding 3L of deionized water, uniformly stirring the mixture, making wet paper through a stainless steel filter screen of 80 meshes, putting the wet paper into a paper sample press, pressing the wet paper under the pressure of 40MPa, and drying the wet paper by using a flat plate dryer at 105 ℃ for 10min, obtaining copper-plated carbon fiber paper with the quantitative amount of about 100g/m 2 . The structure of the copper-coated carbon fiber paper can be seen in fig. 2.
(5) Solid-phase sintering: and (3) putting the copper-plated carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid-phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 40min, so that the high-performance electrode precursor can be obtained, and the structure of the high-performance electrode precursor can be shown in fig. 3.
Example 3
The embodiment comprises the following steps:
(1) pretreatment: the same as in example 1.
(2) Copper electroplating: putting the pretreated carbon fiber filament into a reactor containing CuSO 4 ·5H 2 Electroplating in an electroplating solution containing 20g/L of O, 15g/L of sodium potassium tartrate, 20g/L of disodium ethylene diamine tetraacetate and 4.1g/L of formaldehyde at the electroplating voltage of 2V and the electroplating temperature of 50 ℃ for 100min to obtain the copper-plated carbon fiber filament, wherein the structure of the copper-plated carbon fiber filament can be shown in figure 1.
(3) Cutting into short pieces: the same as in example 1.
(4) Wet papermaking: weighing 0.77g (absolute dry mass) of plant fiber pulp, putting into 2L of deionized water, defibering with a defibering machine at 3000rpm for 10min to obtain pulp slurry, then 3.00g (absolute dry mass) of the copper-plated chopped carbon fiber obtained in the step (3) is weighed and placed into pulp slurry, 1L of deionized water is added, stirring at 300rpm for 3min, adding 24mL of 0.05 wt% PEO dispersant, adding 7.2mL of 0.05 wt% PAM dispersant, stirring with a glass rod for 2min, mixing well to obtain a paper-making suspension, transferring to a sheet-making device, adding 3L deionized water, stirring well, making into wet paper with 80 mesh stainless steel filter screen, pressing in a paper pattern press under 40MPa, then dried with a flat plate dryer at 105 ℃ for 12min to obtain copper-coated carbon fiber paper having a basis weight of about 120 g/m. 2 . The structure of the copper-coated carbon fiber paper can be seen in fig. 2.
(5) Solid-phase sintering: and (3) putting the copper-plated carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid-phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 50min, so that the high-performance electrode precursor can be obtained, and the structure of the high-performance electrode precursor can be shown in fig. 3.
Example 4
The embodiment comprises the following steps:
(1) pretreatment: the same as in example 1.
(2) Copper electroplating: putting the pretreated carbon fiber filament into a reactor containing CuSO 4 ·5H 2 Electroplating in an electroplating solution containing 20g/L of O, 15g/L of sodium potassium tartrate, 20g/L of disodium ethylene diamine tetraacetate and 4.1g/L of formaldehyde at the electroplating voltage of 2V and the electroplating temperature of 50 ℃ for 110min to obtain the copper-plated carbon fiber filament, wherein the structure of the copper-plated carbon fiber filament can be shown in figure 1.
(3) Cutting short: the same as in example 1.
(4) Wet papermaking: weighing 0.94g (absolute dry mass) of plant fiber pulp, putting into 2L of deionized water, defibering with a defibering machine at 3000rpm for 10min to obtain pulp slurry, then 3.77g (absolute dry mass) of the copper-plated chopped carbon fibers obtained in the step (3) are weighed and placed into pulp slurry, 1L of deionized water is added, stirring at 300rpm for 3min, adding 0.05 wt% of PEO dispersant 30mL, adding 0.05 wt% of PAM dispersant 9mL, stirring with a glass rod for 2min, mixing well to obtain papermaking suspension, transferring to a papermaking device, adding 3L of deionized water, stirring well, making into wet paper with 80 mesh stainless steel filter screen, pressing in a paper pattern press under 40MPa, then dried with a flat plate dryer at 105 ℃ for 15min to obtain copper-coated carbon fiber paper having a basis weight of about 150 g/m. 2 . The structure of the copper-coated carbon fiber paper can be seen in fig. 2.
(5) Solid-phase sintering: and (3) putting the copper-plated carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid-phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 60min, so as to obtain the high-performance electrode precursor, and the structure of the high-performance electrode precursor can be referred to fig. 3.
Comparative example 1
The embodiment comprises the following steps:
(1) pretreatment: soaking 12K carbon fiber filaments with the diameter of 6 microns in acetone at normal temperature for 15min, then heating the acetone to 120 ℃, performing reflux treatment in the acetone at the temperature of 120 ℃ for 10h, taking out the carbon fiber filaments, washing the carbon fiber filaments for 2 times by using the acetone, soaking the carbon fiber filaments in absolute ethyl alcohol for 15min, taking out the carbon fiber filaments and washing the carbon fiber filaments by using deionized water; soaking the treated carbon fiber filaments in a roughening solution containing 100g/L of chromium trioxide and 100g/L of sulfuric acid for 8min, taking out the carbon fiber filaments to be washed by deionized water, soaking the carbon fiber filaments in a sodium hydroxide solution of 8g/L for 5min, taking out the carbon fiber filaments to be washed by the deionized water, soaking the carbon fiber filaments in a sensitizing solution containing 0.15g/L of hydrochloric acid and 40g/L of stannous chloride for 20min, taking out the carbon fiber filaments to be soaked in an activating solution of 0.5g/L of palladium chloride for 6min, taking out the carbon fiber filaments to be soaked in 30g/L of sodium hypophosphite for 40s, taking out the carbon fiber filaments to be washed by the deionized water, and placing the carbon fiber filaments in an oven to be dried for 1.5h at 70 ℃.
(2) Cutting short: and (2) cutting the carbon fiber filaments obtained after the pretreatment in the step (1) into short carbon fibers with the length of 6mm by a fiber cutting machine.
(3) Wet papermaking: weighing 0.51g (absolute dry mass) of plant fiber pulp, putting the plant fiber pulp into 2L of deionized water, defibering the plant fiber pulp by using a defibering device at the rotating speed of 3000rpm for 10min to prepare pulp slurry, then weighing 1.0g (absolute dry mass) of the chopped carbon fiber obtained in the step (2) and 1.0g of copper fiber (diameter 25um and length 6mm), putting the chopped carbon fiber and the copper fiber into the pulp slurry, adding 1L of deionized water, stirring the mixture for 3min at the rotating speed of 300rpm, then adding 16mL of 0.05 wt% of PEO dispersant, adding 4.8mL of 0.05 wt% of PAM dispersant, stirring the mixture for 2min by using a glass rod, uniformly mixing the mixture to prepare paper-making suspension, transferring the paper-making suspension to a paper-making machine, adding 3L of deionized water, uniformly stirring the paper-making wet paper, pressing the wet paper by using a stainless steel filter screen of 80 meshes, putting the wet paper into a paper-like press under the pressure of 40MPa, then drying the wet paper for 10min at 105 ℃ by using a flat plate dryer to obtain carbon fiber paper, the quantitative ratio of the polymer is about 80g/m 2 。
(4) Solid-phase sintering: and (4) putting the carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 30min, so as to obtain the carbon fiber/copper fiber mixed electrode precursor.
Comparative example 2
The embodiment comprises the following steps:
(1) pretreatment: soaking 12K carbon fiber filaments with the diameter of 6 microns in acetone at normal temperature for 15min, then heating the acetone to 120 ℃, performing reflux treatment in the acetone at the temperature of 120 ℃ for 10h, taking out the carbon fiber filaments, washing the carbon fiber filaments for 2 times by using the acetone, soaking the carbon fiber filaments in absolute ethyl alcohol for 15min, taking out the carbon fiber filaments and washing the carbon fiber filaments by using deionized water; soaking the treated carbon fiber filaments in a roughening solution containing 100g/L of chromium trioxide and 100g/L of sulfuric acid for 8min, taking out the carbon fiber filaments to be washed by deionized water, soaking the carbon fiber filaments in a sodium hydroxide solution of 8g/L for 5min, taking out the carbon fiber filaments to be washed by the deionized water, soaking the carbon fiber filaments in a sensitizing solution containing 0.15g/L of hydrochloric acid and 40g/L of stannous chloride for 20min, taking out the carbon fiber filaments to be soaked in an activating solution of 0.5g/L of palladium chloride for 6min, taking out the carbon fiber filaments to be soaked in 30g/L of sodium hypophosphite for 40s, taking out the carbon fiber filaments to be washed by the deionized water, and placing the carbon fiber filaments in an oven to be dried for 1.5h at 70 ℃.
(2) Cutting short: and (2) cutting the carbon fiber filaments obtained after the pretreatment in the step (1) into short carbon fibers with the length of 6mm by a fiber cutting machine.
(3) Wet papermaking: weighing 0.51g (absolute dry mass) of plant fiber pulp, putting the plant fiber pulp into 2L of deionized water, defibering the plant fiber pulp by using a defibering device at the rotating speed of 3000rpm for 10min to prepare pulp slurry, then weighing 0.67g (absolute dry mass) of the chopped carbon fiber obtained in the step (2) and 1.33g of copper fiber (diameter 25um and length 6mm) to be put into the pulp slurry, adding 1L of deionized water, stirring the mixture for 3min at the rotating speed of 300rpm, then adding 16mL of 0.05 wt% of PEO dispersant, adding 4.8mL of 0.05 wt% of PAM dispersant, stirring the mixture for 2min by using a glass rod, uniformly mixing the mixture to prepare paper-making suspension, transferring the paper-making suspension to a paper-making machine, adding 3L of deionized water, uniformly stirring the paper-making wet paper, making the wet paper into a paper-making machine through a stainless steel filter screen of 80 meshes, pressing the paper-making machine at the pressure of 40MPa, then drying the wet paper-making machine at 105 ℃ for 10min to obtain carbon fiber paper, the quantitative ratio of the polymer is about 80g/m 2 。
(4) Solid-phase sintering: and (4) putting the carbon fiber paper obtained in the step (4) into a vacuum atmosphere furnace, and performing solid phase sintering in a nitrogen atmosphere, wherein the sintering temperature is 860 ℃ and the sintering time is 30min, so as to obtain the carbon fiber/copper fiber mixed electrode precursor.
Comparative example 3
The embodiment comprises the following steps:
(1) pretreatment: as in comparative example 1.
(2) Cutting short: as in comparative example 1.
(3) Wet papermaking: weighing 0.38g (absolute dry mass) of plant fiber pulp, putting the plant fiber pulp into 2L of deionized water, and defibering the plant fiber pulp for 10min at the rotating speed of 3000rpm by using a defibering device to prepare pulp slurry; weighing 1.50g (absolute dry mass) of the chopped carbon fibers obtained in the step (2), putting the chopped carbon fibers into 1L of deionized water, carrying out ultrasonic treatment for 30min, then mixing the mixture with pulp slurry, then adding 12mL of 0.05 wt% of PEO dispersant, adding 3.6mL of 0.05 wt% of PAM dispersant, stirring the mixture with a glass rod for 2min, uniformly mixing the mixture to prepare papermaking suspension, transferring the papermaking suspension to a papermaking device, adding 3L of deionized water, uniformly stirring, papermaking into wet paper through a stainless steel filter screen of 80 meshes, putting the wet paper into a paper sample presser, pressing the wet paper under the pressure of 40MPa, and then drying the wet paper in a flat plate dryer at 105 ℃ for 10min to prepare a carbon fiber paper precursor, wherein the quantitative amount of the carbon fiber paper precursor is about 60g/m 2 。
(4) Dipping: and (3) soaking the carbon fiber paper precursor obtained in the step (3) for 10s by using phenolic resin with the concentration of 1.5 wt%, taking out, draining, and then drying in an oven at 60 ℃ for 40min to obtain the resin/carbon fiber paper composite.
(5) Hot pressing: and (4) hot-pressing the resin/carbon fiber paper composite obtained in the step (4) by using a flat vulcanizing machine, wherein the hot-pressing pressure is 5MPa, the hot-pressing temperature is 120 ℃, and the hot-pressing time is 10 min.
(6) Carbonizing: and (3) putting the hot-pressed resin/carbon fiber paper composite in the step (5) into a vacuum atmosphere furnace, and carbonizing at 700 ℃ for 30min in a nitrogen atmosphere to obtain the carbon fiber paper.
(7) And (3) retreatment: soaking the paper E obtained in the step (6) in a roughening solution containing 100g/L of chromium trioxide and 100g/L of sulfuric acid for 15min, taking out the paper and washing with deionized water, soaking the paper E in a sodium hydroxide solution of 8g/L for 10min, taking out the paper and washing with deionized water, soaking the paper E in a sensitizing solution containing 0.15g/L of hydrochloric acid and 40g/L of stannous chloride for 30min, taking out the paper E and soaking the paper E in an activating solution of 0.5g/L of palladium chloride for 10min, taking out the paper E and soaking the paper E in 30g/L of sodium hypophosphite for 1min, washing with deionized water, and drying the paper E in an oven at 80 ℃ for 2h to obtain the reprocessed carbon fiber paper.
(8) Copper electroplating: step (7)) Placing the obtained carbon fiber paper after the reprocessing into a paper containing CuSO 4 ·5H 2 Electroplating in an electroplating solution containing 20g/L of O, 15g/L of sodium potassium tartrate, 20g/L of disodium ethylene diamine tetraacetate and 4.1g/L of formaldehyde at the electroplating voltage of 2V and the electroplating temperature of 50 ℃ for 50min to obtain the comparative electrode precursor.
And (3) testing: the thermal conductivity and the electrical resistivity of the electrode precursor were measured using a laser thermal conductivity meter and a resistance meter, respectively. Wherein the laser thermal conductivity meter was tested using a sample having a length and width of 10 mm. The test results are shown in table 1 below.
TABLE 1
| Electrode precursor | Thermal conductivity (W.m) -1 ·K -1 ) | Resistivity (m omega cm) |
| Example 1 | 151.9 | 23.56 |
| Example 2 | 165.1 | 22.95 |
| Example 3 | 184.9 | 22.17 |
| Example 4 | 217.4 | 21.67 |
| Comparative example 1 | 60.2 | 45.57 |
| Comparative example 2 | 65.6 | 37.18 |
| Comparative example 3 | 74.3 | 27.36 |
As can be seen from the results in table 1, the electrode precursors prepared by the methods of examples 1 to 4 have higher thermal conductivity and lower electrical resistivity than those of the comparative examples.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A method for preparing a high-performance electrode precursor by using copper-plated carbon fiber papermaking is characterized by comprising the following steps:
(1) pretreatment: sequentially carrying out desizing treatment, coarsening treatment, neutralizing treatment, sensitizing treatment, activating treatment and reducing treatment on the carbon fiber filaments, washing with deionized water and drying;
(2) copper electroplating: placing the carbon fiber filament pretreated in the step (1) in an electroplating copper solution for electroplating, washing with deionized water after electroplating, and drying to obtain a copper-plated carbon fiber filament;
(3) cutting short: cutting the copper-plated carbon fiber filaments obtained in the step (2) into copper-plated chopped carbon fibers by a fiber cutting machine;
(4) wet papermaking: adding the copper-plated chopped carbon fibers obtained in the step (3) and the pulp subjected to defibering treatment into deionized water, and stirring to prepare slurry; then adding a dispersant, and mixing uniformly to prepare a papermaking suspension; then, screening and papermaking are carried out to obtain wet paper, and the wet paper is placed in a paper pattern presser for pressing and drying to obtain copper-plated carbon fiber paper;
(5) solid-phase sintering: and (5) treating the copper-plated carbon fiber paper obtained in the step (4) in an inert atmosphere by adopting a solid-phase sintering method to obtain an electrode precursor.
2. The method according to claim 1, wherein the carbon fiber filaments of step (1) are 12K carbon fiber filament bundles having a cross-sectional diameter of 5-9 um.
3. The method as claimed in claim 1, wherein the desizing treatment in step (1) is to soak the carbon fiber filaments in acetone at room temperature for 10-20min, then heat the acetone to 110-130 ℃, reflux the carbon fiber filaments in acetone at 110-130 ℃ for more than 6h, then take out the carbon fiber filaments, wash the carbon fiber filaments with acetone for 2 times, soak the carbon fiber filaments in absolute ethyl alcohol for 10-20min, and take out the carbon fiber filaments and wash the carbon fiber filaments with deionized water.
4. The method as claimed in claim 1, wherein the electrolytic copper plating solution of step (2) is CuSO-containing 4 ·5H 2 10-30g/L of O, 10-20g/L of sodium potassium tartrate, 10-30g/L of disodium ethylenediamine tetraacetic acid and 3-7mL/L of formaldehyde, wherein the electroplating voltage is 1-3V, the electroplating temperature is 40-60 ℃, and the electroplating time is more than 20 min.
5. The method as claimed in claim 1, wherein the copper-plated carbon fiber filaments are cut into copper-plated chopped carbon fibers with a length of 2-8mm by the fiber cutter in step (3).
6. The method of claim 1, wherein the defibering treatment in step (4) is carried out by weighing a certain amount of pulp in 1-2L of water, and defibering with a defibering machine at 3000rpm for 5-15 min.
7. The method of claim 1, wherein the dispersing agent of step (4) is PEO and PAM; wherein, the adding amount of PEO is 0.1-0.5% of the weight of the oven dry slurry; the amount of PAM added is 0.05-0.2% of the weight of the oven dried pulp.
8. The method as claimed in claim 1, wherein the solid phase sintering temperature in step (5) is 700-1050 ℃, and the sintering time is 20-90 min.
9. An electrode precursor produced by the method of any one of claims 1 to 8.
10. Use of an electrode precursor according to claim 9 for the preparation of a capacitor.
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