CN115020645B - Composite electrode material, preparation method thereof and solid-state battery - Google Patents
Composite electrode material, preparation method thereof and solid-state battery Download PDFInfo
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- CN115020645B CN115020645B CN202210885581.6A CN202210885581A CN115020645B CN 115020645 B CN115020645 B CN 115020645B CN 202210885581 A CN202210885581 A CN 202210885581A CN 115020645 B CN115020645 B CN 115020645B
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- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 239000007772 electrode material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 96
- 239000002243 precursor Substances 0.000 claims abstract description 71
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 31
- 239000011734 sodium Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 66
- 239000004917 carbon fiber Substances 0.000 claims description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 51
- 239000011265 semifinished product Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920000297 Rayon Polymers 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 3
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a composite electrode material, a preparation method thereof and a solid-state battery, which relate to the technical field of batteries and are used for solving the problems of low safety and short cycle life of a solid-state sodium battery. A method of preparing a composite electrode material, comprising: providing a wet-formed carbon paper precursor; impregnating the carbon paper precursor in resin to obtain a carbon paper precursor impregnated product; carrying out hot press solidification and carbonization operation on the carbon paper precursor impregnation matter to obtain carbon paper; and embedding and depositing sodium sheets on the carbon paper to obtain the composite electrode material. The carbon paper is prepared by a preparation method of a composite electrode material; the invention discloses a composite electrode material, a preparation method thereof and a solid-state battery for preparing the composite electrode material.
Description
Technical Field
The present invention relates to the field of battery technology, and in particular, to a composite electrode material, a method for preparing the same, and a solid-state battery
Background
Most of the current sodium ion batteries use organic liquid electrolyte, and have the safety problems of easy leakage, easy combustion and the like of the electrolyte. The solid-state battery adopts solid electrolyte to replace the traditional organic liquid electrolyte, so that the safety performance is good and the energy density is high.
However, when the negative electrode material is a metal sodium electrode, the volume change is very large in the continuous charge and discharge process, the pulverization failure is easy, and the electrochemical performance and the cycle life of the solid-state battery are reduced. Therefore, it is critical to prepare an electrode material that can improve the safety and cycle life of a solid sodium battery.
Disclosure of Invention
The invention aims to provide a sodium/carbon paper composite electrode material, a preparation method thereof and a solid-state battery, so as to ensure high safety of the composite electrode material and long cycle life.
In order to achieve the above object, the present invention provides a method for preparing a composite electrode material, comprising:
providing a wet-formed carbon paper precursor;
impregnating the carbon paper precursor in resin to obtain a carbon paper precursor impregnated product;
carrying out hot press solidification and carbonization operation on the carbon paper precursor impregnation matter to obtain carbon paper;
and embedding and depositing sodium sheets on the carbon paper to obtain the composite electrode material.
Compared with the prior art, in the preparation method of the composite electrode material, the wet-process formed carbon paper precursor is firstly immersed in resin, then the wet-process formed carbon paper precursor is prepared into current collector carbon paper through hot press solidification and carbonization operation, and finally sodium sheets are embedded and deposited on the carbon paper, so that the obtained composite electrode is a composite body of sodium and carbon paper. And because the carbon paper has higher porosity and specific surface area, the higher porosity can provide a channel for sodium ions, the charge transfer efficiency is improved, the diffusion movement of the carbon paper in the charge-discharge process is accommodated, the volume expansion in the charge-discharge process is accommodated, and the safety is improved. Moreover, the carbon paper precursor is immersed in the resin, so that the carbon fibers overlapped with each other are bonded together, thereby forming a planar stacked structure. In this way, the structure of the obtained composite material is more compact in the subsequent steps, the conductive loops which can be communicated are more, and the mechanical stability, the specific surface area and the conductive performance of the composite material are greatly improved, so that the negative effect caused by the volume change due to the fact that sodium ions are released from the positive electrode material in the charging and discharging process is relieved, and the safety and the cycle life of the solid-state battery are obviously improved.
In a second aspect, the invention further provides a composite electrode material, which is prepared by the preparation method of the composite electrode material.
In a third aspect, the present invention further provides a solid-state battery, including the composite electrode material.
Compared with the prior art, the composite electrode material and the solid-state battery provided by the invention have the same beneficial effects as those of the preparation method of the composite electrode material in the first aspect, and the description is omitted herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
fig. 1 shows a flow chart of the preparation of the composite electrode material provided in this embodiment;
fig. 2 shows a schematic structural diagram of a battery according to an embodiment of the present invention.
Reference numerals:
200-battery, 201-solid electrolyte, 203-positive current collector, 202 a-positive electrode material, 202 b-negative electrode material, 204 a-positive electrode casing, 204 b-negative electrode casing.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. The meaning of "a number" is one or more than one unless specifically defined otherwise.
At present, when a metal sodium electrode is used in a solid sodium battery, sodium ions are deintercalated in the continuous charge and discharge process, and the volume change before and after deintercalation is large, so that the electrode material is easy to pulverize and lose efficacy in the process, and the electrochemical performance and the cycle life of the solid sodium battery are reduced.
In view of the above problems, the preparation method of the composite electrode material provided by the embodiment of the invention can be used for preparing the composite electrode material for improving the safety and the cycle life of the solid sodium battery. Fig. 1 shows a preparation flow chart of a composite electrode material provided by an embodiment of the invention. As shown in fig. 1, the preparation method of the composite electrode material comprises the following steps:
step 101: a wet formed carbon paper precursor is provided.
The carbon paper precursor in the embodiment of the invention is obtained by a wet forming technical means. In the technical means, the carbon fiber and the paper-based fiber are mechanically stirred in the solution at the speed of 600 rpm-1000 rpm for more than 10min to fully disperse the fiber, the fully dispersed fiber is made into paper to form a wet paper web, and finally the wet paper web is dried at the temperature of 95-110 ℃ for 35-40 min to obtain the carbon paper precursor which is obtained in the embodiment of the invention. In order to achieve more thorough interlacing between the fibres, organic compounds are generally added, which contain binders (e.g. polyvinyl alcohol, polyimide) and cationic reinforcing agents (e.g. surfactants).
Step 102: and (3) impregnating the carbon paper precursor into the resin to obtain a carbon paper precursor impregnated product.
Illustratively, the resin functions as an adhesive in embodiments of the present invention. And (3) dipping the carbon paper precursor into resin to bond the carbon fibers which are overlapped with each other, so as to form a plane superposition structure. In this way, the structure of the obtained composite material is more compact in the subsequent steps, and the mechanical stability and the specific surface area of the composite material are greatly improved, so that the negative effect caused by the volume change due to the fact that sodium ions are detached from the positive electrode material in the charging and discharging process is relieved, and the safety and the cycle life of the solid-state battery are remarkably improved. When the phenolic resin is adopted, the residual carbon rate is high, and the conductivity is good, so that the composite material prepared in the subsequent step not only can have a tighter structure, but also can be communicated with more conductive loops, and the conductivity is greatly improved. It should be understood that the resin used in the embodiments of the present invention may be adjusted according to actual requirements, and is not limited herein.
Illustratively, the carbon paper precursor has a basis weight of from 85 g/square meter to 90 g/square meter. In this range, the lower cost can be ensured, the strength, the conductivity and the weight of the formed carbon paper can be ensured to meet the working requirement of the solid sodium battery, and when the ration of the carbon paper precursor is 90 g/square meter, the carbon paper precursor has enough carbon fibers, so that the resin can be fully contacted with the carbon fibers in the steps of impregnating and thermocompression curing in the resin, and the carbon fibers overlapped with each other are bonded, so that a plane superposition structure is formed. Moreover, because the carbon fiber has brittleness, when the carbon fiber is formed by a wet method, an adhesive (such as polyvinyl alcohol) is needed to be added to strengthen the toughness, when the carbon paper precursor is added to be immersed in resin with brittleness, the polyvinyl alcohol can perform synergistic effect with the resin to bond the carbon fiber more tightly, so that the mechanical stability and the specific surface area of the composite material prepared in the subsequent step are greatly improved, the negative effect caused by volume change due to the fact that sodium ions are deintercalated from a positive electrode material in the charging and discharging process is relieved, and the safety and the cycle life of the solid-state battery are obviously improved.
Step 103: and carrying out hot press curing and carbonization operation on the carbon paper precursor impregnation product to obtain a semi-finished product of the composite electrode material.
The carbon paper precursor impregnated matter is subjected to hot press curing before carbonization operation, so that the resin can be fully contacted with the fibers in the carbon paper precursor under the action of hot press before the carbon paper precursor is not converted into carbon paper, and the bonding effect of the carbon fibers overlapped with each other is better. And because of the above, the carbon paper precursor impregnant after hot pressing and curing can be carbonized to bond the carbon fibers in the formed planar stacked structure more tightly. In this way, the mechanical stability, specific surface area and conductivity of the obtained composite material are better in the subsequent steps, so that the purposes of improving the safety and the cycle life of the solid-state battery are achieved.
Step 104: and embedding and depositing the sodium sheet on the semi-finished product of the composite electrode material to obtain the composite electrode material.
Exemplary, the dried semi-finished product of the composite electrode material is punched into small discs with the diameter of 18mm, and then the small discs are put on a button cell electrode shell, and a counter electrode is provided as a metal sodium sheet, at the moment, the diameter of the small discs is 1mA/cm 2 ～2mA/cm 2 And (3) charging and discharging are carried out under constant current density, sodium ions are reduced into metallic sodium in the semi-finished product of the composite electrode material, so that sodium sheets are embedded and deposited on the semi-finished product of the composite electrode material, and the composite electrode which is a composite body of sodium and carbon paper is obtained. And because the carbon paper has higher porosity and specific surface area, the higher porosity can provide a channel for sodium ions, the charge transfer efficiency is improved, the diffusion movement of the carbon paper in the charge and discharge process is accommodated, and the volume expansion in the charge and discharge process is accommodated, so that the purposes of improving the safety and the cycle life of the solid sodium battery are achieved.
In an alternative, the carbon paper precursor includes a carbon fiber raw material, polyvinyl alcohol, a surfactant, and polyethylene oxide.
Illustratively, the carbon fiber feedstock is comprised of carbon fibers and paper-based fibers, including at least one of viscose, cellulose nanofibrils, and carbon fibers. The carbon fiber is at least one of polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, wherein the polyacrylonitrile-based carbon fiber has good structural and functional characteristics and high yield; pitch-based carbon fibers are popular, but the carbon yield after carbonization exceeds 80%, and thus are good choices of carbon fiber types.
The mass ratio of the viscose fiber to the carbon fiber to the cellulose nano-filament is (10-15): (84-88): (1-2). Adding proper amount of water at 600-1000 rpm, stirring mechanically for over 10min, and dispersing the carbon fiber material. When the carbon fiber raw material accounts for 0.1-0.15% of the mass of the mixture of the carbon fiber raw material and water, the carbon fiber raw material can be fully dispersed into single fibers, and the occurrence of the phenomenon of fiber aggregation is avoided. The length of the carbon fiber is 5 mm-6 mm, and the resistivity is 1mΩ/cm-10 mΩ/cm. The length of the viscose fiber is 3 mm-4 mm, at this time, the filling effect of the viscose fiber is better, and the formed paper is more uniform.
Illustratively, when the mass ratio of polyethylene oxide, surfactant and polyvinyl alcohol is (2.5-3): (1-1.5) and (2.5-3), under the proportion, the polyethylene oxide, the surfactant and the polyvinyl alcohol are cooperated to lead the interweaving among the carbon fiber raw materials to be more sufficient, thereby ensuring that the composite electrode material formed in the subsequent step has good mechanical stability and specific surface area.
Illustratively, the surfactant is at least one of tween-80, turkish red oil, and glyceryl oleate. Carbon fibers have hydrophobicity, so that agglomeration is easy to occur under the soaking of water and uniform dispersion is difficult, and therefore, a surfactant needs to be added to the carbon fibers as a dispersing agent of the carbon fibers to promote the sufficient dispersion of the carbon fibers in water. When the carbon paper precursor is immersed in the resin, the surfactant is used as the dispersing agent of the carbon fiber, so that the carbon fiber can be fully contacted with the resin in the immersing process, and the phenomenon that only part of the carbon fiber is immersed in the resin due to carbon fiber aggregation is avoided. Based on this, in a subsequent step, the resin may bond the carbon fibers dispersed into individual ones to form a planar stacked structure. Thus, the structure of the obtained composite material is more compact, and the mechanical stability, specific surface area and conductivity of the composite material are also improved. When the surfactant is Tween-80, the addition amount is 0.02-0.04% of the mass of the carbon paper precursor before drying, and the produced dispersing effect is best.
By way of example, the polyvinyl alcohol with the mass percentage of 10% contained in the carbon paper precursor can improve the toughness of the carbon paper through the better strong adhesion, thereby ensuring the better mechanical property and the durability of the composite electrode material prepared in the subsequent steps. When polyvinyl alcohol with the molecular weight of 17-21 ten thousand is selected, the addition amount is 0.1-0.15% of the mass of the carbon paper precursor before drying, the toughness improvement effect on the carbon paper is best.
Illustratively, the carbon paper precursor contains polyethylene oxide with a molecular weight of 600-700 ten thousand, and the addition amount of the polyethylene oxide accounts for 0.1-0.2% of the mass of the carbon paper precursor before drying. Polyethylene oxide is a water-soluble resin, and can be used as a dispersing agent to play a role in dispersing together with a surfactant, so that the dispersing effect of the carbon paper precursor is improved. The polyethylene oxide, the surfactant and the polyvinyl alcohol contained in the carbon paper precursor cooperate to enable the interweaving among the carbon fiber raw materials to be more sufficient, so that the composite electrode material formed in the subsequent steps is ensured to have good mechanical stability and specific surface area.
In an alternative mode, the reaction temperature of the hot press solidification is 135-150 ℃, the reaction pressure is 10-15 MPa, and the reaction time is 40-50 min; the reaction temperature of carbonization is 1350-1500 ℃, the heating rate is 20-30 ℃/min, and the reaction time is 7-8 h.
The carbon paper precursor impregnant is placed in a flat vulcanizing machine, and hot-pressed for 40-50 min under the conditions of 135-150 ℃ and 10-15 MPa, so that gas impurities in the carbon fiber can be discharged in time, the impregnated resin can better contact the carbon fiber, the density of the extruded semi-finished product of the composite electrode material can be obviously improved, and the performance of the composite material is further improved. And then using a vacuum tube furnace to heat treat the carbon paper for 7-8 hours at 1350-1500 ℃ and 20-30 ℃/min under the condition of introducing protective gas (such as nitrogen), so that the carbon content in the semi-finished product of the composite electrode material is remarkably improved, and the semi-finished product of the composite electrode material has higher conductivity, mechanical stability and specific surface area.
The embodiment of the invention also provides a composite electrode material, which is prepared by the preparation method of the composite electrode material.
Illustratively, the composite electrode material is essentially a composite of sodium and carbon paper. And because the carbon paper has higher porosity and specific surface area, the higher porosity can provide a channel for sodium ions, the charge transfer efficiency is improved, the diffusion movement of the carbon paper in the charge-discharge process is accommodated, the volume expansion in the charge-discharge process is accommodated, and the safety is improved.
The embodiment of the invention provides a solid-state battery which can comprise the composite electrode material provided by the embodiment of the invention, so that the safety of the composite electrode material is high, and the cycle life is long. It should be understood that the composite electrode material may be defined as a negative electrode material in which carbon paper may act as a current collector for the negative electrode of the solid state sodium battery. The solid state sodium battery may further include a positive electrode case, a positive electrode material, a positive electrode current collector, a negative electrode case, and a solid state electrolyte between the positive electrode material and the negative electrode material, and may be defined as having opposing first and second surfaces, the positive electrode material being located between the positive electrode current collector and the first surface, the positive electrode current collector being located between the positive electrode case and the positive electrode material, the negative electrode material being located between the negative electrode case and the second surface. Fig. 2 shows a schematic view of a battery according to an embodiment of the present invention, and as shown in fig. 2, a battery 200 according to an embodiment of the present invention includes a solid electrolyte 201, a positive electrode current collector 203, a positive electrode material 202a, a negative electrode material 202b, a positive electrode case 204a, and a negative electrode case 204b, which are distributed on both sides of the solid electrolyte 201.
The invention is further illustrated below with reference to examples.
Example 1
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
first, preparing a carbon paper precursor: 10 parts by weight of viscose fiber with the length of 3mm, 2 parts by weight of cellulose nanofibrils, 88 parts by weight of polyacrylonitrile-based carbon fiber with the length of 6mm and the resistivity of 10mΩ/cm are weighed, the raw materials of the carbon fiber are added into a dispersing barrel with a stirrer, 568 parts of water is added to enable the total mass fraction of the viscose fiber, the cellulose nanofibrils and the polyacrylonitrile-based carbon fiber to be 0.15%, stirring is started, and the rotating speed is 700rpm. Adding Tween-80 with the content of 0.04wt percent, adding polyethylene oxide with the content of 0.12wt percent (the molecular weight is 700 ten thousand), adding a polyvinyl alcohol solution with the content of 0.12wt percent (the molecular weight is 21 ten thousand and the concentration is 10 percent) after the carbon fiber raw material is completely dispersed into single fibers, mechanically stirring for 10 minutes, preparing a wet paper web by wet forming equipment, and drying for 30 minutes by a baking oven at 110 ℃ to prepare the carbon paper precursor with the quantitative of 90 g/square meter.
Secondly, preparing a carbon paper precursor impregnant: and (3) immersing the carbon paper precursor in the resin, using ultrasonic equipment to assist in ultrasonic treatment, immersing for 1min, taking out and drying to obtain the carbon paper precursor immersed product.
Thirdly, preparing a semi-finished product of the composite electrode material: and (3) placing the carbon paper precursor impregnant in a flat vulcanizing machine, hot-pressing for 45min at 140 ℃ and 10MPa, and then performing heat treatment on the carbon paper precursor impregnant for 8h at a speed of 1500 ℃ and 30 ℃/min by using a vacuum tube furnace under the protection of nitrogen, so as to obtain a semi-finished product of the composite electrode material.
Fourth, preparing a composite electrode material: and (3) punching the dried semi-finished product of the composite electrode material into a small wafer with the diameter of 18mm, putting the small wafer on an electrode shell of a button cell, and setting a counter electrode as a metal sodium sheet. At this time, at 1mA/cm 2 And (3) charging and discharging under constant current density, so that the sodium sheet is embedded and deposited on the semi-finished product of the composite electrode material, and the composite electrode material is obtained.
Example two
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
first, preparing a carbon paper precursor: 13 parts by weight of viscose fiber with the length of 3mm, 1 part by weight of cellulose nanofibril, 84 parts by weight of polyacrylonitrile-based carbon fiber with the length of 6mm and the resistivity of 10mΩ/cm are weighed, the carbon fiber raw material is added into a dispersing barrel with a stirrer, 570 parts of water is added to enable the total mass fraction of the viscose fiber, the cellulose nanofibril and the polyacrylonitrile-based carbon fiber to be 0.15%, stirring is started, the rotating speed is 700rpm, tween-80 with the content of 0.04wt% is firstly added, then polyethylene oxide with the content of 0.10wt% (with the molecular weight of 600 ten thousand) is added, after the carbon fiber raw material is completely dispersed into single fiber, polyvinyl alcohol solution with the content of 0.10wt% (with the molecular weight of 19 ten thousand and the concentration of 10%) is added, after mechanical stirring is carried out for 10min, wet paper web is manufactured through wet forming equipment, and drying is carried out for 35min at 95 ℃ to prepare a carbon paper precursor with the ration of 85 g/square meter.
Secondly, preparing a carbon paper precursor impregnant: and (3) immersing the carbon paper precursor in the resin, using ultrasonic equipment to assist in ultrasonic treatment, immersing for 2 minutes, taking out and drying to obtain the carbon paper precursor immersed product.
Thirdly, preparing a semi-finished product of the composite electrode material: and (3) placing the carbon paper precursor impregnant in a flat vulcanizing machine, hot-pressing for 50min at 135 ℃ and 10MPa, and then performing heat treatment on the carbon paper precursor impregnant for 7h at a speed of 1500 ℃ and 20 ℃/min by using a vacuum tube furnace under the protection of nitrogen, so as to obtain a semi-finished product of the composite electrode material.
Fourth, preparing a composite electrode material: and (3) punching the dried semi-finished product of the composite electrode material into a small wafer with the diameter of 18mm, putting the small wafer on an electrode shell of a button cell, and setting a counter electrode as a metal sodium sheet. At this time, at 2mA/cm 2 And (3) charging and discharging under constant current density, so that the sodium sheet is embedded and deposited on the semi-finished product of the composite electrode material, and the composite electrode material is obtained.
Example III
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
first, preparing a carbon paper precursor: 10 parts by weight of viscose fiber with the length of 3mm, 2 parts by weight of cellulose nanofibrils, 88 parts by weight of pitch-based carbon fiber with the length of 6mm and the resistivity of 6mΩ/cm are weighed, the carbon fiber raw material is added into a dispersing barrel with a stirrer, 600 parts of water is added to enable the total mass fraction of the viscose fiber, the cellulose nanofibrils and the polyacrylonitrile-based carbon fiber to be 0.10%, stirring is started, the rotating speed is 700rpm, turkey red oil with the content of 0.05wt% is firstly added, then polyethylene oxide with the content of 0.20wt% (with the molecular weight of 700 ten thousand) is added, after the carbon fiber raw material is completely dispersed into single fiber, polyvinyl alcohol solution with the content of 0.15wt% (with the molecular weight of 21 ten thousand and the concentration of 10%) is added, after mechanical stirring for 10min, wet forming equipment is used for drying for 40min at 100 ℃ to prepare a carbon paper precursor with the ration of 87 g/square meter.
Secondly, preparing a carbon paper precursor impregnant: and (3) immersing the carbon paper precursor in the resin, using ultrasonic equipment to assist in ultrasonic treatment, immersing for 1min, taking out and drying to obtain the carbon paper precursor immersed product.
Thirdly, preparing a semi-finished product of the composite electrode material: and (3) placing the carbon paper precursor impregnant in a flat vulcanizing machine, hot-pressing for 45min at 140 ℃ and 15MPa, and then performing heat treatment on the carbon paper precursor impregnant for 8h at a speed of 1500 ℃ and 25 ℃/min by using a vacuum tube furnace under the protection of nitrogen, so as to obtain a semi-finished product of the composite electrode material.
Fourth, preparing a composite electrode material: and (3) punching the dried semi-finished product of the composite electrode material into a small wafer with the diameter of 18mm, putting the small wafer on an electrode shell of a button cell, and setting a counter electrode as a metal sodium sheet. At this time, at 1mA/cm 2 And (3) charging and discharging under constant current density, so that the sodium sheet is embedded and deposited on the semi-finished product of the composite electrode material, and the composite electrode material is obtained.
Example IV
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
first, preparing a carbon paper precursor: 15 parts by weight of viscose fiber with the length of 3mm, 2 parts by weight of cellulose nanofibrils, 44 parts by weight of asphalt-based carbon fiber with the length of 6mm and the resistivity of 6mΩ/cm, 44 parts by weight of polyacrylonitrile-based carbon fiber with the length of 6mm and the resistivity of 6mΩ/cm are weighed, the raw materials of the carbon fiber are added into a dispersing barrel with a stirrer, 800 parts of water is added so that the total mass fraction of the viscose fiber, the cellulose nanofibrils and the polyacrylonitrile-based carbon fiber is 0.15%, stirring is started, the rotating speed is 700rpm, 0.02wt% of oleic glyceride is firstly added, then 0.12wt% of polyethylene oxide (with the molecular weight of 700 ten thousand) is added, after the raw materials of the carbon fiber are completely dispersed into single fiber, 0.15wt% of polyvinyl alcohol solution (with the molecular weight of 20 ten thousand and the concentration of 10%) is added, after mechanical stirring for 10min, wet paper is manufactured by wet forming equipment, and the wet paper is dried by a baking oven for 35min at 100 ℃ to prepare the precursor of carbon precursor with the quantitative quantity of 85 g/square meter.
Secondly, preparing a carbon paper precursor impregnant: and (3) immersing the carbon paper precursor in the resin, using ultrasonic equipment to assist in ultrasonic treatment, immersing for 1min, taking out and drying to obtain the carbon paper precursor immersed product.
Thirdly, preparing a semi-finished product of the composite electrode material: and (3) placing the carbon paper precursor impregnant in a flat vulcanizing machine, hot-pressing for 45min at 140 ℃ and 15MPa, and then performing heat treatment on the carbon paper precursor impregnant for 8h at a speed of 1350 ℃ and 25 ℃/min by using a vacuum tube furnace under the protection of nitrogen, so as to obtain a semi-finished product of the composite electrode material.
Fourth, preparing a composite electrode material: and (3) punching the dried semi-finished product of the composite electrode material into a small wafer with the diameter of 18mm, putting the small wafer on an electrode shell of a button cell, and setting a counter electrode as a metal sodium sheet. At this time, at 2mA/cm 2 And (3) charging and discharging under constant current density, so that the sodium sheet is embedded and deposited on the semi-finished product of the composite electrode material, and the composite electrode material is obtained.
The foregoing is merely a specific embodiment of the invention, and it will be apparent that various modifications and combinations thereof can be made without departing from the spirit and scope of the invention. Accordingly, the specification and drawings are merely exemplary illustrations of the present invention as defined in the appended claims and are considered to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily think of changes or substitutions within the technical scope of the present disclosure, and the present disclosure is intended to be covered by the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A method of preparing a composite electrode material, comprising:
providing a wet-formed carbon paper precursor; the carbon paper precursor comprises carbon fiber raw materials, polyvinyl alcohol, a surfactant and polyethylene oxide; the surfactant is at least one of Tween-80, turkish red oil and glyceryl oleate; the mass ratio of the polyethylene oxide to the surfactant to the polyvinyl alcohol is (2.5-3): (1-1.5): (2.5-3); the carbon fiber raw material comprises at least one of viscose fiber, cellulose nanofibrils and carbon fiber; the carbon fiber is at least one of polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, the length of the carbon fiber is 5 mm-6 mm, the resistivity of the carbon fiber is 1mΩ/cm-10 mΩ/cm, and the length of the viscose fiber is 3 mm-4 mm; the mass ratio of the viscose fiber to the carbon fiber to the cellulose nanofibrils is (10-15): (84-88): (1-2);
impregnating the carbon paper precursor into resin to obtain a carbon paper precursor impregnated material;
carrying out hot press solidification and carbonization operation on the carbon paper precursor impregnation matter to obtain a semi-finished product of the composite electrode material;
at 1mA/cm 2 ~2mA/cm 2 And (3) carrying out charge and discharge under constant current density, and embedding and depositing sodium sheets on the semi-finished product of the composite electrode material to obtain the composite electrode material.
2. The method for preparing the composite electrode material according to claim 1, wherein the carbon paper precursor is impregnated into the resin, and the carbon paper precursor has a quantitative ratio of 85g per square meter to 90g per square meter; and/or the number of the groups of groups,
the reaction temperature of the hot press solidification is 135-150 ℃, the reaction pressure is 10-15 MPa, and the reaction time is 40-50 min; the carbonization reaction temperature is 1350-1500 ℃, the heating rate is 20-30 ℃/min, and the reaction time is 7-8 h.
3. A composite electrode material, characterized in that the composite electrode material is prepared by the preparation method of the composite electrode material according to any one of claims 1-2.
4. A solid state battery comprising the composite electrode material of claim 3.
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