CN110415994B - Three-dimensional nano composite electrode material for electrochemical energy storage and preparation method thereof - Google Patents

Three-dimensional nano composite electrode material for electrochemical energy storage and preparation method thereof Download PDF

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CN110415994B
CN110415994B CN201910664209.0A CN201910664209A CN110415994B CN 110415994 B CN110415994 B CN 110415994B CN 201910664209 A CN201910664209 A CN 201910664209A CN 110415994 B CN110415994 B CN 110415994B
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carbon
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composite electrode
graphene oxide
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CN110415994A (en
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卢文
成方
王从敏
仇武忻
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Kunming Yunda New Energy Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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    • H01M4/00—Electrodes
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a three-dimensional nano composite electrode material for electrochemical energy storage and a preparation method thereof. The three-dimensional nano composite electrode material for electrochemical energy storage is formed by compounding two or more nano carbon materials, a conductive agent and a binder with a super capacitor electrode material or a lithium ion battery electrode material. The preparation method of the three-dimensional nano composite electrode material for electrochemical energy storage comprises the preparation of the three-dimensional nano composite electrode for a super capacitor and the preparation of the three-dimensional nano composite electrode for a lithium ion battery. The invention introduces two or more than two nano-carbon materials and a conductive agent to carry out composite modification on the electrode material of the super capacitor or the lithium ion battery, and fully exerts the synergistic effect of the various nano-carbon materials and the conductive agent through optimizing the composite method, so that the three-dimensional nano-composite electrode material has the advantages of high assembly density, good conductivity, excellent rate property and electrochemical stability, simple preparation process, environmental protection, low cost and suitability for large-scale production.

Description

Three-dimensional nano composite electrode material for electrochemical energy storage and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a novel high-performance three-dimensional nano composite electrode material for a super capacitor or a lithium ion battery and a preparation method thereof.
Background
Since the 20 th century, the development of economy has been rapidly advanced, the resources are about to be exhausted, the pollution is becoming serious, and the search for novel renewable energy sources capable of replacing fossil energy sources such as petroleum, coal, natural gas and the like is urgent. Meanwhile, the rapid development of new energy technologies brings about an urgent need for new energy storage technologies.
Super capacitor (also called electrochemical capacitor) is a new energy storage element between conventional capacitor and chemical battery which is developed and developed in recent decades at home and abroad. Due to its higher power density (10) 3 ～10 4 W kg -1 ) And ultra-long cycle life (up to tens of thousands of times), and a wide working temperature range (-40 to 70 ℃), and the super capacitor has been widely applied to the fields of transportation, renewable energy, industrial and consumer electronics products, and the like. At present, electrode materials of commercial supercapacitors are mainly porous carbon materials with high specific surface area, such as Activated Carbon (AC) powder, activated carbon cloth, activated carbon fibers, carbon aerogel, porous graphite, porous hard carbon, mesoporous carbon and the like, and the porous carbon materials are used as mainstream electrode materials of the supercapacitors due to the advantages of mature preparation process, abundant raw materials, low production cost and the like. With the continuous improvement of the performance requirements of the market on the super capacitor, the defects of poor conductivity, low assembly density, poor cycling stability and the like of the porous carbon material are increasingly highlighted, so that the capacitor energy based on the porous carbon electrode materialLow density, poor power performance, and limited service life. In addition, the conductive agent adopted in the preparation process of the electrode material of the current commercial super capacitor is mainly conductive carbon black (such as SP), and the conductivity of the conductive agent has certain limitation, so that the conductivity of the electrode material prepared by the conductive agent is relatively poor. Therefore, how to increase the assembly density of the porous carbon electrode for the supercapacitor and improve the conductivity of the porous carbon electrode for the supercapacitor and prepare the electrode material for the supercapacitor with high conductivity, high assembly density and high cycling stability is a technical problem which needs to be solved urgently.
In recent years, with the rise of nanocarbon materials (Graphene), carbon Nanotubes (CNT), carbon Nanofibers (CNF), etc.), their advantages such as excellent physicochemical properties, excellent electrical conductivity, structural nanocrystallization, etc. make them a research hotspot in the field of new materials, and a great deal of research efforts have been directed to the use of pure nanocarbon materials as supercapacitor electrode materials (CN 106653389A, CN101271969A, etc.). However, the extremely low packing density, complicated preparation process and high production cost of the nanocarbon material make it difficult to be applied to a large-scale and commercial scale. Therefore, research on preparing a novel nano carbon-porous carbon composite electrode by combining a nano carbon material used as a conductive additive with a porous carbon material and performing composite modification becomes a hot topic in the field of electrode materials of supercapacitors in recent years. For example, patents CN106847834A, CN102214515A, CN1942985A and the like respectively disclose methods for preparing composite electrodes from activated carbon materials and nanocarbon materials such as graphene, carbon nanotubes, carbon nanofibers and the like, and the performance of the composite electrode materials prepared by these methods is improved, but such methods for improving the performance of the composite electrodes by compositely modifying a single nanocarbon material and a porous carbon electrode have limitations, and are still difficult to meet the requirements of the market on high-performance supercapacitors.
Compared with a super capacitor, the lithium ion battery as another emerging energy storage element has relatively higher working voltage and energy density, so that the lithium ion battery is widely applied to the fields of rail transit transportation, new energy automobiles and the like. However, the charge-discharge process of the lithium ion battery electrode material mainly involves reversible intercalation/deintercalation of lithium ions, so that the power performance and the service life of the lithium ion battery are obviously lower than those of a super capacitor, and the key point for improving the power characteristic and the service life of the lithium ion battery is to improve the conductivity and the cycle stability of the lithium ion battery electrode material. Common lithium ion battery positive electrode materials mainly include: lithium iron phosphate (LFP), lithium Cobaltate (LCO), lithium Manganate (LMO), lithium Nickel Manganese Oxide (LNMO), ternary material (NCM, NCA) etc. negative pole material mainly has: graphite, hard carbon, soft carbon, mesocarbon microbeads, silicon/carbon composites, lithium Titanate (LTO), and the like. At present, conductive agents adopted in the preparation process of electrode materials of commercial lithium ion batteries are mainly conductive carbon black (such as SP) and conductive graphite (such as KS 6), and the conductivity of the conductive agents is obviously lower than that of nano carbon materials, so that the conductivity of the electrode materials prepared by the conductive agents is relatively poor. Therefore, the nano carbon material is used as a conductive additive to be compositely modified with the lithium ion battery electrode material, so that the conductivity of the composite electrode is improved, the power characteristic of the lithium ion battery is further improved, and the nano carbon material has high grindability and large market application potential. Based on this, patents CN105047874A and CN102569796A respectively disclose a method for preparing a composite electrode by performing composite modification on a lithium iron phosphate material, graphene and a carbon nanotube, and patents CN107706397A and CN101764219A respectively disclose a method for preparing a composite electrode by performing composite modification on a ternary material, a graphite material and a carbon nanotube, and rate performance of a lithium ion battery nanocarbon composite electrode material prepared by such methods is improved to a certain extent.
Disclosure of Invention
The first purpose of the invention is to provide a three-dimensional nanocomposite electrode material for electrochemical energy storage, which has high assembly density, good conductivity, rate characteristics and excellent electrochemical stability; the second purpose is to provide a method for preparing the three-dimensional nano composite electrode of the super capacitor of the three-dimensional nano composite electrode material for electrochemical energy storage, which has simple preparation process and low cost and is suitable for large-scale production; the third objective is to provide a method for preparing a lithium ion three-dimensional nanocomposite electrode of a three-dimensional nanocomposite electrode material for electrochemical energy storage.
The first object of the present invention is achieved by: the three-dimensional nano composite electrode material is prepared by compounding two or more nano carbon materials, a conductive agent and a binder with a porous carbon electrode material of a super capacitor or an electrode material of a lithium ion battery.
The second object of the present invention is achieved by: the preparation method of the supercapacitor three-dimensional nano composite electrode made of the three-dimensional nano composite electrode material comprises the steps of graphite oxide preparation, graphene in-situ coating porous carbon material preparation, carbon nanofiber dispersion liquid preparation and supercapacitor three-dimensional nano composite electrode preparation, and is characterized by specifically comprising the following steps of:
A. preparing graphite oxide: according to an improved Hummers method, potassium permanganate with a mass ratio of 3 to crystalline flake graphite and concentrated sulfuric acid with a volume/mass ratio of 23 ml;
B. preparing a graphene in-situ coated porous carbon material: ultrasonically stripping the graphite oxide prepared in the step A in an aqueous solution for 3-5 hours to form graphene oxide and simultaneously coat porous carbon in situ, reducing the obtained graphene oxide by hydrazine hydrate, and separating, washing and drying to prepare the porous carbon material coated with the reduced graphene oxide in situ;
C. preparing a carbon nanofiber dispersion liquid: acidizing the carbon nanofiber by using mixed acid of concentrated sulfuric acid/concentrated nitric acid with the volume ratio of 3;
D. preparing a three-dimensional nano composite electrode of the super capacitor: according to the mass ratio, 50-97.99% of porous carbon electrode material, 0.01-10% of nano carbon material, 1-20% of conductive agent, 1-20% of binder and 0.01-10% of carbon nano fiber dispersion liquid prepared in the step C are mixed; or adding 50-97.99% of reduced graphene oxide in-situ coated porous carbon material prepared in the step B, 1-20% of conductive agent, 1-20% of binder and 0.01-10% of carbon nanofiber dispersion liquid prepared in the step C or 0.01-10% of nano carbon material into aqueous solution according to the mass ratio, stirring at high speed in vacuum to form electrode slurry, then uniformly coating the electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain the three-dimensional nano composite electrode of the supercapacitor.
The surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or polyvinylpyrrolidone; the water solution is ultrapure water, deionized water or distilled water.
The third object of the present invention is achieved by: the preparation method of the three-dimensional nano composite electrode of the lithium ion battery comprises the steps of preparing the graphene in-situ coated lithium ion battery electrode material, preparing graphene oxide dispersion liquid, preparing reduced graphene oxide dispersion liquid and preparing the three-dimensional nano composite electrode of the lithium ion battery, and is characterized by specifically comprising the following steps of:
A. preparing a graphene in-situ coated lithium ion battery electrode material: ultrasonically stripping graphite oxide in ultrapure water for 3-4 h, reducing the obtained graphene oxide by using hydrazine hydrate, coating the lithium ion battery electrode material in situ, separating, washing and drying to prepare the reduced graphene oxide in-situ coated lithium ion battery electrode material;
B. preparing a graphene oxide dispersion liquid: carrying out ultrasonic stripping and dispersion on the graphite oxide in N-methyl pyrrolidone to prepare a graphene oxide dispersion liquid;
C. preparing a reduced graphene oxide dispersion liquid: carrying out high-temperature reduction on graphite oxide in the atmosphere of nitrogen or argon, taking N-methyl pyrrolidone as a solution, carrying out ultrasonic stripping on the obtained reduced graphene oxide for 60-120 min, and dispersing to prepare a reduced graphene oxide dispersion liquid;
D. preparing a three-dimensional nano composite electrode of the lithium ion battery: 50-97.99% of lithium ion battery electrode material, 0.01-10% of nano carbon material, 1-20% of conductive agent, 1-20% of binder and 0.01-10% of graphene oxide dispersion liquid prepared in the step B or 0.01-10% of reduced graphene oxide dispersion liquid prepared in the step C according to the mass ratio; or adding 50-97.99% of graphene in-situ coated lithium ion battery electrode material prepared in the step A, 0.01-10% of nano carbon material, 1-20% of conductive agent and 1-20% of binder into N-methyl pyrrolidone solution together according to the mass ratio, stirring at high speed in vacuum to form electrode slurry, then uniformly coating the electrode slurry on the surface of a current collector, and drying, rolling and cutting to obtain the three-dimensional nano composite electrode of the lithium ion battery.
The invention is based on a multi-element nano carbon composite system, namely, a porous carbon electrode material for a supercapacitor or an electrode material for a lithium ion battery is subjected to composite modification by introducing two or more nano carbon materials and a conductive agent, so that the synergistic effect of the various nano carbon materials and the conductive agent is fully exerted. The three-dimensional nano composite electrode material for the super capacitor and the lithium ion battery has the advantages of high assembly density, good conductivity, excellent rate characteristic and electrochemical stability. The super capacitor and the lithium ion battery based on the high-performance novel three-dimensional nano composite electrode material for the super capacitor or the lithium ion battery have higher energy density, power density and cycle service life, and further meet the market demand for the high-energy density/high-power density super capacitor or the lithium ion battery. The method disclosed by the invention is simple in preparation process, environment-friendly, low in cost and suitable for industrial production, and is a novel method for preparing a high-performance novel three-dimensional nano composite electrode material for a super capacitor or a lithium ion battery, which is easier to realize industrialization.
Drawings
FIG. 1 is a high power SEM image of novel three-dimensional nanocomposite supercapacitor electrodes prepared from example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2) (1-a), AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2) (1-b), AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3) (1-c)).
FIG. 2 is a high-power scanning electron microscope image of conventional energy-type (2-a) and conventional power-type (2-b) activated carbon electrodes prepared from comparative experimental example 1.
Fig. 3 is an AC impedance graph of a novel three-dimensional nanocomposite electrode for a supercapacitor prepared from example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), (AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2)), and a conventional energy-type activated carbon electrode prepared from comparative experiment 1.
Fig. 4 is an AC impedance diagram of a novel three-dimensional nanocomposite electrode for a supercapacitor prepared from example 1 (AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) and a conventional power-type activated carbon electrode prepared from comparative experimental example 1.
Fig. 5 is a graph showing rate curves of the supercapacitor novel three-dimensional nanocomposite electrodes prepared from example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), (AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2)), and the conventional energy-type activated carbon electrode prepared from comparative experiment 1.
Fig. 6 is a graph of rate of multiplying power of the novel three-dimensional nanocomposite supercapacitor electrode prepared in example 1 (AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) and the conventional power-type activated carbon electrode prepared in comparative experimental example 1.
Fig. 7 is a cyclic voltammogram of a novel three-dimensional nanocomposite electrode for a supercapacitor prepared from example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), (AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2)), and a conventional energy-type activated carbon electrode prepared from comparative experiment 1.
Fig. 8 is a cyclic voltammogram of the novel three-dimensional nanocomposite electrode for supercapacitor prepared from example 1 (AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) and the conventional power-type activated carbon electrode prepared from comparative experimental example 1.
Fig. 9 is a cycle life graph of a novel three-dimensional nanocomposite supercapacitor electrode prepared from example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), (AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2)), and a conventional energy-type activated carbon electrode prepared from comparative experiment 1.
Fig. 10 is a cycle life graph of a novel three-dimensional nanocomposite electrode for a supercapacitor prepared from example 1 (AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) and a conventional power-type activated carbon electrode prepared from comparative experimental example 1.
Fig. 11 is a high-power scanning electron microscope image of the novel three-dimensional nanocomposite electrode for lithium ion batteries prepared from example 2 (reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (aqueous phase) composite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/3/1/4) (11-a), the graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) composite electrode (LFP/GO/CNT/SP/KS 6/PVDF = 90/1/3/1/4) (11-b), the reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) composite electrode (LFP/rgcnt/SP/KS 6/PVDF = 90/1/3/1/4) (11-c)), and the lithium ion battery prepared from comparative experimental example 2 using a conventional iron phosphate electrode for GO (11-d).
Fig. 12 is a graph showing comparative analysis of ac impedance of the novel three-dimensional nanocomposite electrode for lithium ion batteries prepared in example 2 and the conventional lithium iron phosphate electrode for lithium ion batteries prepared in comparative experimental example 2.
Fig. 13 is a graph showing comparative analysis of rate curves of the novel three-dimensional nanocomposite electrode for lithium ion batteries prepared in example 2 and the conventional lithium iron phosphate electrode for lithium ion batteries prepared in comparative experiment 2.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, which are provided for the purpose of illustrating the technical solutions of the present invention and are not intended to limit the present invention in any way, and all changes or modifications made based on the teachings of the present invention are within the scope of the present invention.
The three-dimensional nano composite electrode material for electrochemical energy storage is prepared by compounding two or more nano carbon materials, a conductive agent and a binder with a porous carbon electrode material of a super capacitor or an electrode material of a lithium ion battery.
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.01-10% of nano carbon material, 1-20% of conductive agent, 1-20% of binder, 50-97.99% of porous carbon electrode material of super capacitor or 50-97.99% of electrode material of lithium ion battery.
The nano carbon material is two or more of Carbon Nano Tube (CNT), graphene (Graphene) and Carbon Nano Fiber (CNF); the carbon nano tube is a single-walled carbon nano tube and/or a multi-walled carbon nano tube, and the graphene is single-layer graphene and/or multi-layer graphene.
The conductive agent is one or more of carbon black, acetylene black, conductive graphite and conductive carbon fiber; the binder is one or more of sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR), butadiene rubber (BDR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA) and acrylic resin (AAP).
The porous carbon electrode material of the supercapacitor is one or more of activated carbon powder, activated carbon cloth, activated carbon fiber, carbon aerogel, porous graphite, porous hard carbon and mesoporous carbon.
The positive electrode material of the lithium ion battery electrode material is one or more of lithium iron phosphate (LFP), lithium Cobaltate (LCO), lithium Manganate (LMO), lithium Nickel Manganese (LNMO) or ternary materials (NCM, NCA); the negative electrode material is one or more of graphite, hard carbon, soft carbon, mesocarbon microbeads, silicon/carbon composite material and Lithium Titanate (LTO).
The electrode material is in a buckled disc type, a cylindrical winding type, a laminated square type or a laminated special type.
Example 1, preparation and testing of a high-performance novel three-dimensional nanocomposite electrode for a supercapacitor according to the present invention:
1. the invention discloses a preparation method of a high-performance novel three-dimensional nano composite electrode for a super capacitor
1.1 Preparation of AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2) three-dimensional nano composite electrode
A. Preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) mixed solution
Accurately weighing 1g of sodium carboxymethylcellulose (CMC) solid powder, adding the powder into a 100 ml beaker, then weighing 99 g of ultrapure water, adding magnetons with the length of 2 cm into the beaker, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100 r/min, and stirring for 12 hours at room temperature to prepare a CMC aqueous solution with the mass fraction of 1%. Accurately weighing the CMC aqueous solution with the mass ratio of 2 wt% (12 g) and adding the CMC aqueous solution into a 50 ml vacuum stirring tank, then adding an SBR aqueous solution with the mass fraction of 50 wt% with the mass ratio of 3 wt% (0.36 g), setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring for 30 min at room temperature to prepare a uniformly dispersed CMC and SBR mixed solution.
B. Coating of Carbon Nanotubes (CNTs) on the surface of Activated Carbon (AC) particles
Accurately weighing water-based CNT slurry with the Carbon Nano Tube (CNT) content of 5 wt% and the mass ratio of 3.125 wt% (3.75 g), adding the water-based CNT slurry into the mixed solution prepared in the step A, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring at room temperature for 30 min to prepare a uniformly dispersed mixed solution of the Carbon Nano Tube (CNT), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); accurately weighing Activated Carbon (AC) solid powder with the mass ratio of 90 wt% (5.4 g), adding the powder into the mixed solution for three times, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min each time, and preparing mixed slurry with CNT uniformly coated on the surface of AC particles.
C. Preparation of Carbon Nanofiber (CNF) dispersion
Accurately weighing Carbon Nanofiber (CNF) powder with the mass ratio of 0.625 wt% (0.0375 g) into a 100 ml beaker, adding 20 ml of mixed acid of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3.
D. Preparation of AC/CNT/CNF/SP/SBR/CMC = 90/3.125/0.625/1.25/3/2 three-dimensional nanocomposite electrode
Adding the CNF dispersion liquid prepared in the step C into the mixed slurry prepared in the step B, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min, adding a conductive agent SP with the mass ratio of 1.25 wt% (0.075 g), setting the rotating speed of the vacuum stirrer to be 500 r/min, continuously stirring at room temperature for 60 min to prepare three-dimensional nano composite electrode slurry, vacuumizing and standing the composite electrode slurry for 10 min, filtering by using a 100-mesh filter screen, coating the slurry on a corroded aluminum foil current collector, drying at 60 ℃ for 3 h, rolling, punching into a circular pole piece with the diameter of 12 mm by using a slicing machine, and then drying the pole piece at 60 ℃ for 12 h in vacuum to prepare the novel three-dimensional nano composite electrode for the super capacitor, wherein the electrode component is AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2) (shown in figure 1-a).
Preparation of (90/2.75/1/1.25/3/2) three-dimensional nano composite electrode
A. Preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) mixed solution
A uniformly dispersed CMC and SBR mixed solution was prepared as in example 1, step A.
B. Coating of Carbon Nanotubes (CNTs) and reduced graphene oxide (rGO) on the surface of Activated Carbon (AC) particles
a) Preparing graphite oxide: the modified Hummers method is used for preparing graphite oxide: adding 3 g of flake graphite into 69 ml of concentrated sulfuric acid under the ice bath condition, and then adding 9 g of potassium permanganate (purity: 99.5 wt%) into the flake graphiteOxidizing graphite (potassium permanganate is slowly added to ensure that the temperature of the system is lower than 20 ℃), removing an ice bath, heating to 35 +/-3 ℃ in a water bath and keeping for 30 min, slowly adding 138 mL of ultrapure water to ensure that the temperature of the system reaches 98 ℃ and keeps for 15 min, continuously adding 420 mL of warm water at 40 ℃, adding 3 mL of 30 wt% hydrogen peroxide to reduce the residual oxidant, strongly stirring the obtained solution at room temperature for 24 h, repeatedly washing with 5 wt% of HCl solution and ultrapure water until no SO exists in the supernatant fluid 4 2- (with BaCl) 2 Inspection), obtaining a bright yellow graphite oxide solution, centrifuging the obtained graphite oxide solution, and drying in vacuum at 80 ℃ for 12 h to obtain a graphite oxide solid.
b) Coating of Carbon Nanotubes (CNTs) and reduced graphene oxide (rGO) on the surface of Activated Carbon (AC) particles: accurately weighing 1 wt% graphite oxide (0.1 g) prepared in step B a) of 1.2 in example 1, adding the graphite oxide into a 250 ml beaker, pouring 100 g of ultrapure water, covering the mouth of the beaker with a film, putting the beaker into an ultrasonic machine, leading the water level of the ultrasonic machine to be lower than the water level in the beaker, adding 5 ml of 80 wt% hydrazine hydrate after 30 min of ultrasonic treatment, adding 0.25 wt% (0.5 g) of water-based CNT slurry with the CNT content of 5 wt% after reacting for two minutes, adding 90 wt% (9 g) of AC after 30 min of ultrasonic treatment, stirring, and then carrying out ultrasonic treatment for 4 h. Filtering with a Buchner funnel, washing off excessive hydrazine hydrate with ultrapure water, drying in a forced air drying oven at 60 ℃ for 3 h, transferring to a vacuum oven, drying at 60 ℃ and-0.8 MPa for 12 h, and grinding after drying to obtain the AC/rGO/CNT composite material.
C. Preparation of AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2) electrode slurry
Accurately weighing water-based CNT slurry with the CNT content of 5 wt% and the mass ratio of 2.5 wt% (3 g) and adding the water-based CNT slurry into the mixed solution of the CMC and the SBR prepared in the step A, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring for 30 min at room temperature, adding the AC/rGO/CNT composite material prepared in the step B) with the mass ratio of 90 wt% (5.475 g) in three times, setting the rotating speed of the vacuum stirrer to be 500 r/min, stirring for 40 min at room temperature, then adding a conductive agent SP with the mass ratio of 1.25 wt% (0.075 g), setting the rotating speed of the vacuum stirrer to be 500 r/min, and stirring for 60 min to prepare the AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2) three-dimensional nano composite electrode slurry.
D. Preparation of AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2) three-dimensional nano composite electrode
Accurately weighing 4 g of ultrapure water, adding the ultrapure water into the composite electrode slurry prepared in the step C, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring the mixture at room temperature for 30 min, adjusting the solid content of the slurry to be 24%, vacuumizing and standing the mixture for 10 min, filtering the mixture by using a 100-mesh sieve, coating the obtained slurry on a corroded aluminum foil current collector, drying the slurry at 60 ℃ for 3 h, rolling the slurry, punching the slurry into a circular pole piece with the diameter of 12 mm by using a slicing machine, and then drying the pole piece at 60 ℃ for 12 h in a vacuum manner to prepare the three-dimensional nano composite electrode (shown in figure 1-b) for the supercapacitor, wherein the electrode component is AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2).
(78.75/1.25/1.25/8.75/7/3) preparation of three-dimensional nanocomposite electrode
A. Preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) mixed solution
A CMC aqueous solution with a mass fraction of 1% was prepared according to the method of step a of 1.1 in example 1, and then a CMC aqueous solution with a mass ratio of 3 wt% (18 g) and an SBR aqueous solution with a mass ratio of 7 wt% (0.84 g) with a mass fraction of 50 wt% were weighed to prepare a uniformly dispersed CMC and SBR mixed solution according to the method of step a of 1.1 in example 1.
B. In-situ coating of reduced graphene oxide (rGO) on the surface of Activated Carbon (AC) particles
Accurately weighing 1.25 wt% (0.4 g) of graphite oxide prepared by the method of step B a) in example 1, adding the graphite oxide into a beaker filled with 100 ml of ultrapure water, ultrasonically stripping for 30 min, slowly adding 78.75 wt% (25.2 g) of activated carbon powder, carrying out in-situ coating of graphene oxide on the surfaces of the activated carbon particles, carrying out ultrasonic treatment for 90 min, adding 15 ml of 80 wt% hydrazine hydrate, ultrasonically reducing for 60 min, filtering, carrying out vacuum drying at 60 ℃ for 12 h to obtain an activated carbon material (AC/rGO) coated with reduced graphene oxide, accurately weighing 80 wt% (4.8 g) of AC/rGO solid powder, adding the solid powder into the mixed solution prepared in step A for three times, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring for 30 min at room temperature every time to prepare the mixed slurry of AC/rGO, CMC and SBR.
C. Preparation of Carbon Nanofiber (CNF) dispersion
CNF was weighed accurately at a mass ratio of 1.25 wt% (0.09 g) to prepare a uniform CNF dispersion according to the method of step C1.1 in example 1.
D. Preparation of AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3) three-dimensional nano composite electrode
Adding the CNF dispersion liquid prepared in the step C into the mixed slurry prepared in the step B, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min, adding a conductive agent SP with the mass ratio of 8.75 wt% (0.525 g), setting the rotating speed of the vacuum stirrer to be 500 r/min, stirring at room temperature for 60 min to prepare three-dimensional nano composite electrode slurry for a supercapacitor, vacuumizing and standing the slurry for 10 min, filtering by using a 100-mesh filter screen, coating the slurry on a corroded aluminum foil current collector, drying at 60 ℃ for 3 h, rolling, punching into a circular pole piece with the diameter of 12 mm by using a slicing machine, and then drying the pole piece at 60 ℃ for 12 h in vacuum to prepare the three-dimensional nano composite electrode for the supercapacitor with the electrode component of AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3) (shown in figure 1-C).
(97.99/0.005/0.005/1/0.6/0.4) preparation of three-dimensional nanocomposite electrode
A. Preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) mixed solution
Accurately weighing 1g of sodium carboxymethylcellulose (CMC) solid powder, adding the powder into a 100 ml beaker, then weighing 99 g of ultrapure water, adding magnetons with the length of 2 cm into the beaker, sealing the mouth of the beaker by using a plastic film and a rubber ring, placing the beaker on a magnetic stirrer, setting the rotating speed to be 100 r/min, and stirring for 12 hours at room temperature to prepare a CMC aqueous solution with the mass fraction of 1%. Accurately weighing the CMC aqueous solution with the mass ratio of 0.4 wt% (2.4 g) and 10 g of ultrapure water, adding the CMC aqueous solution and 10 g of ultrapure water into a 50 ml vacuum stirring tank, then adding an SBR aqueous solution with the mass ratio of 0.6 wt% (0.072 g) and the mass fraction of 50 wt%, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring for 30 min at room temperature to prepare a uniformly dispersed CMC-SBR mixed solution.
B. Coating of Carbon Nanotubes (CNTs) on the surface of Activated Carbon (AC) particles
Accurately weighing water-based CNT slurry with the Carbon Nano Tube (CNT) content of 5 wt% and the mass ratio of 0.005 wt% (0.006 g), adding the water-based CNT slurry into the mixed solution prepared in the step A, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring at room temperature for 30 min to prepare a uniformly dispersed mixed solution of the Carbon Nano Tube (CNT), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); and (2) accurately weighing Activated Carbon (AC) solid powder with the mass ratio of 97.99 wt% (5.8794 g), adding the powder into the mixed solution for three times, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min each time, and preparing mixed slurry with CNT uniformly coated on the surface of AC particles.
C. Preparation of Carbon Nanofiber (CNF) dispersion
Accurately weighing Carbon Nanofiber (CNF) powder with the mass ratio of 0.005 wt% (0.0003 g) into a 100 ml beaker, adding 20 ml of mixed acid of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3.
D. Preparation of AC/CNT/CNF/SP/SBR/CMC = 97.99/0.005/0.005/1/0.6/0.4 three-dimensional nanocomposite electrode
And C, adding the CNF dispersion liquid prepared in the step C into the mixed slurry prepared in the step B, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min, adding a conductive agent SP with the mass ratio of 1 wt% (0.06 g), setting the rotating speed of the vacuum stirrer to be 500 r/min, continuously stirring at room temperature for 60 min to prepare three-dimensional nano-composite electrode slurry, vacuumizing and standing the composite electrode slurry for 10 min, filtering by using a 100-mesh filter screen, coating the slurry on a corroded aluminum foil current collector, drying at 60 ℃ for 3 h, rolling, punching into a circular pole piece with the diameter of 12 mm by using a slicer, and then drying the pole piece at 60 ℃ for 12 h in vacuum to prepare the novel three-dimensional nano-composite electrode for the capacitor, wherein the electrode component is AC/CNT/CNF/SP/SBR/CMC (97.99/0.005/0.005/1/0.6/0.4).
Preparation of (50/4/6/20/12/8) three-dimensional nano composite electrode
A. Preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) mixed solution
Accurately weighing 8 wt% (0.48 g) of sodium carboxymethylcellulose (CMC) solid powder and 17 g of ultrapure water, adding the powder and 17 g of ultrapure water into a 50 ml vacuum stirring tank, setting the rotating speed of the vacuum stirrer to be 500 r/min, stirring for 60 min at room temperature, adding 12 wt% (1.44 g) of SBR aqueous solution with the mass fraction of 50 wt%, setting the rotating speed of the vacuum stirrer to be 500 r/min, and stirring for 30 min at room temperature to prepare the uniformly dispersed CMC-SBR mixed solution.
B. Coating of Carbon Nanotubes (CNTs) on the surface of Activated Carbon (AC) particles
Accurately weighing water-based CNT slurry with the Carbon Nano Tube (CNT) content of 5 wt% and the mass ratio of 4 wt% (4.8 g), adding the water-based CNT slurry into the mixed solution prepared in the step A, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring at room temperature for 30 min to prepare a uniformly dispersed mixed solution of the Carbon Nano Tube (CNT), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR); accurately weighing 50 wt% (3 g) of Activated Carbon (AC) solid powder, adding into the mixed solution for three times, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min each time, and preparing mixed slurry with CNT uniformly coated on the surface of AC particles.
C. Preparation of Carbon Nanofiber (CNF) dispersion
Accurately weighing Carbon Nanofiber (CNF) powder with the mass ratio of 6 wt% (0.36 g) into a 100 ml beaker, then adding 20 ml of mixed acid of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 5, placing a magneton with the length of 2 cm, sealing the opening of the beaker by using a plastic film and a rubber ring, placing the beaker into a magnetic stirring constant-temperature water bath, setting the rotation speed to be 60 r/min, stirring for 3 h at 60 ℃, then centrifugally cleaning to be neutral (PH = 7) by using ultrapure water, adding the cleaned CNF into the beaker filled with 5 g of ultrapure water, then adding 20 mM/L (0.025 g) of Sodium Dodecyl Benzene Sulfonate (SDBS) serving as a surfactant, and performing ultrasonic dispersion for 120 min to obtain a uniform CNF dispersion liquid.
D. Preparation of AC/CNT/CNF/SP/SBR/CMC = 50/4/6/20/12/8 three-dimensional nanocomposite electrode
And C, adding the CNF dispersion liquid prepared in the step C into the mixed slurry prepared in the step B, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring for 30 min at room temperature, adding a conductive agent SP with the mass ratio of 20 wt% (1.2 g), setting the rotating speed of the vacuum stirrer to be 500 r/min, continuously stirring for 60 min at room temperature to prepare three-dimensional nano composite electrode slurry, vacuumizing and standing for 10 min, filtering by using a 100-mesh filter screen, coating the slurry on a corroded aluminum foil current collector, drying for 3 h at 60 ℃, rolling, punching into a circular pole piece with the diameter of 12 mm by using a slicing machine, and then drying the pole piece for 12 h at 60 ℃ in vacuum to prepare the novel super-electric three-dimensional nano composite electrode with the electrode component of AC/CNT/CNF/SP/SBR/CMC (50/4/6/20/12/8).
2. Test of novel three-dimensional nano composite electrode for super capacitor
2.1 high Power Scanning Electron Microscopy (SEM) test
The novel three-dimensional nanocomposite electrode for a supercapacitor prepared from example 1 above: the characterization test of the morphological characteristics of AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2), AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3) is carried out by a high power Scanning Electron Microscope (SEM) (as shown in the attached figures 1-a,1-b and 1-c). The test result shows that: in the composite electrode, CNT can be uniformly wound on the surface of AC particles, graphene sheets form tight coating on the surface of AC particles, CNF can play a role in connecting different particles, and a nano carbon material (CNT + CNF or CNT + rGO or rGO + CNF) and conductive particles SP form an efficient three-dimensional conductive network together.
2.2 electrochemical performance test:
2.2.1 encapsulation
In the control of oxygen (<0.1 ppm) and water (<0.1 ppm) of the electrode, the high-performance novel three-dimensional nanocomposite electrode for supercapacitor of example 1, a LIR2025 battery case, a cellulose acetate separator, and 1M [ TEA ] were charged into a glove box][BF 4 ]The button type super capacitor is assembled by the ACN electrolyte and used for electrochemical performance test after standing for 1 h at room temperature.
2.2.2 electrochemical Performance test
a. And (3) testing alternating current impedance: and (3) carrying out an alternating current impedance test on the button type super capacitor packaged in the step 2.2.1 at an open circuit voltage by adopting an alternating current amplitude of 10 mV within a frequency range of 100 kHz-10 mHz (as shown in attached figures 3 and 4). Test results show that due to the full play of the synergistic effect of the nano carbon material and the formation of the efficient three-dimensional conductive network in the composite electrode, the charge transfer resistance and the diffusion resistance of the composite electrode are obviously reduced, and the conductivity is obviously improved.
b. And (3) rate testing: the button-type super capacitor packaged in the step 2.2.1 adopts 0.5-80 Ag of voltage in the range of 0-2.7V -1 The current density of (a) was tested for rate capability (as shown in figures 5 and 6). The test result shows that: due to the full play of the synergistic effect of the nano-carbon material and the formation of the efficient three-dimensional conductive network in the composite electrode, the rate capability of the composite electrode is greatly improved to 80A g -1 At the current density of (a), the three novel three-dimensional nanocomposite electrodes prepared in example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2), AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) have high capacity retention rates of 71.92%, 87.28%, and 79.54%, respectively, and exhibit excellent rate characteristics.
c. Cyclic voltammetry testing: the button-type super capacitor packaged in the step 2.2.1 is arranged inIn the voltage range of 0-2.7V, 500 mV S is adopted -1 Cyclic voltammetry was performed at the sweep rate of (c) (as shown in fig. 7, 8). The test result shows that: due to the full play of the synergistic effect of the nano-carbon material and the formation of the efficient three-dimensional conductive network in the composite electrode, the voltammetry curve of the composite electrode is 500 mV S -1 The rectangular shape is kept well under the large scanning speed, and the excellent quick response characteristic is shown.
d. And (3) testing the cycle life: the button-type super capacitor packaged in the step 2.2.1 adopts 10 Ag in the voltage range of 0-2.7V -1 The current density of (a) was subjected to a cycle life test (as shown in fig. 9 and 10). The test result shows that: due to the full play of the synergistic effect of the nano-carbon material and the formation of the efficient three-dimensional conductive network in the composite electrode, the composite electrode shows excellent cycle stability. At 10 ag -1 At the current density of (a), the novel three-dimensional nanocomposite electrode prepared in example 1 (AC/CNT/CNF/SP/SBR/CMC (90/3.125/0.625/1.25/3/2), and AC/CNT/rGO/SP/SBR/CMC (90/2.75/1/1.25/3/2)) respectively have high capacity retention rates of 86.37% and 79.44% after 30000 cycles, and the novel three-dimensional nanocomposite electrode prepared in example 1 (AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/8.75/7/3)) has a high capacity retention rate of 91.25% after 15000 cycles.
Embodiment 2, preparation and test of a high-performance novel three-dimensional nanocomposite electrode for a lithium ion battery according to the present invention:
1. preparation of high-performance novel three-dimensional nano composite electrode for lithium ion battery
1.1 preparation of reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (aqueous phase) three-dimensional nanocomposite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4)
A. Preparation of graphite oxide
The preparation of graphite oxide was carried out as in 1.2 step B a) of example 1.
B. Preparation of LFP/rGO (90/1) composite:
adding 100 mL of ultrapure water and 10 mL of 80 wt% water and hydrazine solution into a 250 mL beaker, adding 1 wt% (0.2 g) graphite oxide prepared in the step A into the solution, performing ultrasonic dispersion for 10 min, adding 90 wt% (18 g) LFP material, continuing ultrasonic dispersion for 4 h, washing with ultrapure water, filtering, and performing vacuum drying at 80 ℃ for 12 h to obtain the LFP/rGO (90/1) composite material.
C. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 electrode paste
Adding 20 mL of NMP into a 50 mL vacuum stirring tank, weighing PVDF solid with the mass ratio of 4 wt% (0.8 g) and adding the PVDF solid into the NMP solution, stirring for 90 min, adding NMP slurry with the mass ratio of 1 wt% (4 g) of CNT (the mass fraction is 5 wt%), stirring for 60 min, adding 3 wt% (0.6 g) of conductive agent SP and 1 wt% (0.2 g) of conductive agent KS6, stirring for 60 min, adding the LFP/rGO composite material prepared in the step B with the mass ratio of 91 wt% (18.2 g) in 4 times, and stirring for 30 min every time to obtain the LFP/rGO/CNT/SP/PVDF 6/PVDF = 90/1/3/1/4 electrode slurry.
D. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 composite electrode
And D, vacuumizing and standing the electrode slurry prepared in the step C for 10 min, filtering the electrode slurry by using a 120-mesh sieve, uniformly coating the obtained slurry on an aluminum foil, drying the aluminum foil at 80 ℃ for 2 h, rolling the aluminum foil, punching the aluminum foil into a circular pole piece with the diameter of 14 mm by using a slicer, and then drying the pole piece at 120 ℃ for 12 h in vacuum to obtain the three-dimensional nano composite electrode (shown in figure 11-a) of the reduced graphene oxide/carbon nano tube coated lithium iron phosphate (water phase) (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/3/1/1/4).
Preparation of graphene oxide/carbon nanotube coated lithium iron phosphate (organic phase) three-dimensional nanocomposite electrode (LFP/GO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4)
A. Preparing a graphene oxide dispersion liquid:
a60 mL brown bottle was charged with 10 mL of NMP solution, and 1 wt% (0.2 g) of graphite oxide prepared according to the method of 1.2 step B a) of example 1 was added to the above solution, and after ultrasonic dispersion for 60 min, a dispersion of graphene oxide was formed.
B. LFP/GO/CNT/SP/KS6/PVDF = 90/1/1/3/1/4) electrode paste preparation
Adding 10 mL of NMP into a 50 mL vacuum stirring tank, weighing PVDF solid with the mass ratio of 4 wt% (0.8 g) and adding the PVDF solid into the NMP solution, stirring for 90 min to completely dissolve the PVDF, adding the graphene oxide dispersion liquid prepared in the step A into the stirring tank, stirring for 60 min, adding NMP slurry with the mass ratio of 1 wt% (4 g) of CNT (with the mass fraction of 5 wt%), continuing stirring for 60 min, respectively adding 3 wt% (0.6 g) of conductive agent SP and 1 wt% (0.2 g) of conductive agent KS6, stirring for 60 min, then adding 90 wt% (18 g) of LFP positive electrode material in 4 times, and stirring for 30 min each time to prepare LFP/GO/SP/KS 6/PVDF =90/1/1/3/1/4 electrode slurry.
C. Preparation of LFP/GO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 composite electrode
The electrode slurry was used to prepare an electrode according to the method of step D in example 2, which was described as step 1.1, to obtain a three-dimensional nanocomposite electrode (shown in fig. 11-b) of graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) (LFP/GO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4).
Preparation of reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) three-dimensional nano composite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4)
A. Preparation of reduced graphene oxide
1g of graphite oxide prepared by the method of step two B a) of 1.2 in example 1 was accurately weighed, placed in a porcelain boat, placed in a tube furnace, and heated in a nitrogen atmosphere (gas flow: 100 mL/min), heating to 800 ℃ from room temperature of 25 ℃ at the heating rate of 5 ℃/min, keeping for 1 h, naturally cooling to room temperature, and collecting the material to obtain the reduced graphene oxide powder.
B. Preparation of reduced graphene oxide dispersion liquid
And (3) adding 10 mL of NMP solution into a 60 mL brown bottle, adding 1 wt% (0.2 g) of reduced graphene oxide powder prepared in the step (A) into the solution, and performing ultrasonic dispersion for 60 min to prepare a reduced graphene oxide dispersion liquid.
C. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 electrode paste
Preparation of electrode paste was performed as in 1.2 step B of example 2 to prepare LFP/rGO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 electrode paste.
D. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =90/1/1/3/1/4 composite electrode
The electrode slurry was used to prepare an electrode by the method of step D of example 2, 1.1, to obtain a reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4) three-dimensional nanocomposite electrode (as shown in fig. 11-c).
Preparation of reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (aqueous phase) three-dimensional nanocomposite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 97.99/0.005/0.005/0.75/0.25/1)
A. Preparation of graphite oxide
The preparation of graphite oxide was carried out as in 1.2 step B a) of example 1.
B. Preparation of LFP/rGO (90/1) composite:
and (2) adding 100 mL of ultrapure water into a 250 mL beaker, adding 0.5 mL of 80 wt% water and hydrazine solution, adding the graphite oxide prepared in the step (A) with the mass ratio of 0.005 wt% (0.001 g) into the solution, performing ultrasonic dispersion for 10 min, adding an LFP material with the mass ratio of 97.99 wt% (19.598 g), continuing ultrasonic dispersion for 3 h, washing with the ultrapure water, filtering, and performing vacuum drying at 80 ℃ for 12 h to obtain the LFP/rGO (97.99/0.005) composite material.
C. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =97.99/0.005/0.005/0.75/0.25/1 electrode paste
Adding 20 mL of NMP into a 50 mL vacuum stirring tank, weighing 1 wt% (0.2 g) of PVDF solid, adding the PVDF solid into the NMP solution, stirring for 90 min, adding 0.005 wt% (0.1 g) of CNT-containing NMP slurry (mass fraction is 5 wt%), stirring for 60 min, adding 0.75 wt% (0.15 g) of SP and 0.25 wt% (0.05 g) of KS6, stirring for 60 min, adding the LFP/rGO composite material prepared in the step B in a mass ratio of 97.995 wt% (19.599 g) for 4 times, and stirring for 30 min each time to obtain the LFP/rGO/SP/KS 6/PVDF =97.99/0.005/0.005/0.75/0.25/1 electrode slurry.
D. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =97.99/0.005/0.005/0.75/0.25/1 composite electrode
And D, vacuumizing and standing the electrode slurry prepared in the step C for 10 min, filtering the electrode slurry by using a 120-mesh sieve, uniformly coating the obtained slurry on an aluminum foil, drying the aluminum foil at 80 ℃ for 2 h, rolling the aluminum foil, punching the aluminum foil into a circular pole piece with the diameter of 14 mm by using a slicing machine, and then drying the pole piece at 120 ℃ for 12 h in vacuum to obtain the reduced graphene oxide/carbon nanotube coated lithium iron phosphate (water phase) (LFP/rGO/CNT/SP/KS 6/PVDF = 97.99/0.005/0.005/0.75/0.25/1) three-dimensional nano composite electrode.
Preparation of reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) three-dimensional nanocomposite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 50/6/4/15/5/20)
A. Preparation of reduced graphene oxide
Graphite oxide prepared according to the method of step two B a) of 1.2 in example 1 in a mass ratio of 6 wt% (1.2 g) was accurately weighed and placed in a porcelain boat, and placed in a tube furnace under a nitrogen atmosphere (gas flow: 100 mL/min), heating to 800 ℃ from room temperature of 25 ℃ at the heating rate of 5 ℃/min, keeping for 1 h, naturally cooling to room temperature, and collecting the material to obtain the reduced graphene oxide powder.
B. Preparation of reduced graphene oxide dispersion liquid
And (3) adding 10 mL of NMP solution into a 60 mL brown bottle, adding the reduced graphene oxide powder prepared in the step (A) into the solution, and performing ultrasonic dispersion for 120 min to prepare a dispersion liquid of the reduced graphene oxide.
C. Preparation of LFP/rGO/CNT/SP/KS6/PVDF =50/6/4/15/5/20 electrode paste
Adding 10 mL of NMP into a 50 mL vacuum stirring tank, weighing PVDF solid with the mass ratio of 20 wt% (4 g) and adding the PVDF solid into the NMP solution, stirring for 90 min to completely dissolve the PVDF, adding the graphene oxide dispersion liquid prepared in the step A into the stirring tank, stirring for 60 min, adding NMP slurry with the mass ratio of 4 wt% (16 g) of CNT (with the mass fraction of 5 wt%), continuing stirring for 60 min, respectively adding 15 wt% (3 g) of conductive agent SP and 5 wt% (1 g) of conductive agent KS6, stirring for 60 min, then adding 50 wt% (10 g) of LFP positive electrode material in 4 times, and stirring for 30 min each time to prepare LFP/GO/CNT/SP/KS6/PVDF =50/6/4/15/5/20 electrode slurry.
D. Preparation of LFP/GO/CNT/SP/KS6/PVDF =50/6/4/15/5/20 composite electrode
The electrode slurry was used to prepare an electrode according to the method of step D of example 2 1.1, to prepare a three-dimensional nanocomposite electrode of graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) (LFP/GO/CNT/SP/KS 6/PVDF = 50/6/4/15/5/20).
2. Testing of novel three-dimensional nanocomposite electrode for lithium ion battery
2.1 high power Scanning Electron Microscope (SEM) testing
The novel three-dimensional nanocomposite electrode for lithium ion batteries prepared in example 2 (reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (aqueous phase) composite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/3/1/4), graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) (LFP/GO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4), and reduced graphene oxide/carbon nanotube-coated lithium iron phosphate (organic phase) (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/1/3/1/4)) were subjected to characterization test of morphological characteristics by using a high power Scanning Electron Microscope (SEM) (as shown in fig. 11-a,11-b, 11-c). The test result shows that: in the composite electrode, the graphene sheet layer can form tight coating on the surface of the LFP, the CNT can be uniformly dispersed among LFP particles and plays a role in connecting different LFP particles, and the nanocarbon material (CNT + rGO or CNT + GO) and the conductive particles SP and KS6 form an efficient three-dimensional conductive network together.
Electrochemical Performance test
2.2.1 encapsulation
In the control of oxygen (A)<0.1 ppm) and water (<0.1 ppm) in a glove box, the high-performance novel three-dimensional nanocomposite electrode (as the positive electrode) for the lithium ion battery prepared in example 2 was used,Lithium sheet (as cathode), LIR2025 battery case, PP/PE/PP diaphragm and 1M LiPF 6 The electrolyte of the EC-EMC-DMC (volume ratio is 1.
2.2.2 electrochemical Performance test
a. And (3) testing alternating current impedance: and (3) carrying out an alternating current impedance test on the button lithium ion battery packaged in the step 2.2.1 under the open circuit voltage by adopting the alternating current amplitude of 10 mV within the frequency range of 100 kHz-1 mHz (as shown in figure 12). The test result shows that the charge transfer resistance of the composite electrode is obviously reduced and the conductivity is obviously improved due to the full play of the synergistic effect of the nano carbon material and the formation of the efficient three-dimensional conductive network in the composite electrode.
b. And (3) rate testing: the button lithium ion battery packaged in the step 2.2.1 is charged at 0.2C under the room temperature condition in the voltage range of 2-4V, and is subjected to discharge tests of different multiplying factors of 0.2C, 1C, 2C, 3C, 5C, 7C, 10C and the like respectively, and the cycle is performed for 5 times at each multiplying factor (as shown in figure 13). The test result shows that: the rate capability of the composite electrode is greatly improved due to the full exertion of the synergistic effect of the nanocarbon materials and the formation of the efficient three-dimensional conductive network in the composite electrode, and the three novel three-dimensional nanocomposite electrodes (reduced graphene oxide/carbon nanotube coated lithium iron phosphate (aqueous phase) composite electrode (LFP/rGO/CNT/SP/KS 6/PVDF = 90/1/3/1/4) and the reduced graphene oxide/carbon nanotube coated lithium iron phosphate (organic phase) (LFP/GO/CNT/SP/KS 6/PVDF = 90/1/3/1/4) prepared in example 2 respectively have 138.94 mAh g at a current density of 1C and have a current density of 138.94 mAh g at a current density of 1C -1 、135.73 mAh g -1 、137.49 mAh g -1 The capacity retention rates of the three composite electrodes are 47%, 41% and 46% respectively (as shown in fig. 13) under the large current density of 7C, and the composite electrode shows relatively excellent rate characteristics.
Example 3
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.005% of Carbon Nano Tube (CNT), 0.005% of Carbon Nano Fiber (CNF) or Graphene (Graphene), 1% of carbon black, 1% of Styrene Butadiene Rubber (SBR) binder and 97.99% of activated carbon powder. The inventive supercapacitor was prepared according to the procedure used in example 1.
Example 4
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 5% of Carbon Nanofiber (CNF), 5% of Carbon Nanotube (CNT) or Graphene (Graphene), 20% of acetylene black, 20% of butadiene rubber (BDR) binder and 50% of activated carbon fiber. The supercapacitor of the invention was prepared according to the procedure used in example 1.
Example 5
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 2% of Carbon Nano Tube (CNT), 3% of Graphene (Graphene), 7% of carbon black, 3% of conductive graphite, 5% of polyvinyl alcohol (PVA), 5% of polyvinylidene fluoride (PVDF) binder and 75% of activated carbon powder. The supercapacitor of the invention was prepared according to the procedure used in example 1.
Example 6
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 1% of Carbon Nanofiber (CNF), 2% of Carbon Nanotube (CNT), 3% of carbon black, 5% of conductive carbon fiber, 4% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 5% of Polytetrafluoroethylene (PTFE), 5% of polyvinyl alcohol (PVA), 15% of carbon aerogel, 25% of porous graphite and 30% of mesoporous carbon. The inventive supercapacitor was prepared according to the procedure used in example 1.
Example 7
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.5% of Graphene (Graphene), 0.5% of Carbon Nanofiber (CNF), 1.5% of Carbon Nanotube (CNT), 1.5% of carbon black, 2.5% of conductive graphite, 3.5% of conductive carbon fiber, 3% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 3% of sodium carboxymethyl cellulose (CMC), 4% of polyvinyl alcohol (PVA), 6% of acrylic acid resin (AAP), 12% of activated carbon cloth, 35% of activated carbon fiber and 22% of porous hard carbon. The inventive supercapacitor was prepared according to the procedure used in example 1.
Example 8
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.8% of Graphene (Graphene), 0.2% of Carbon Nanofiber (CNF), 1.0% of Carbon Nanotube (CNT), 1.0% of carbon black, 1.0% of conductive graphite, 1.5% of conductive carbon fiber, 1.5% of acetylene black, 1% of polyvinylidene fluoride (PVDF), 3% of Polytetrafluoroethylene (PTFE), 2% of sodium carboxymethylcellulose (CMC), 1% of polyvinyl alcohol (PVA), 2% of acrylic resin (AAP), 15% of activated carbon powder, 18% of activated carbon cloth, 28% of activated carbon fiber, 12% of porous graphite and 11% of carbon aerogel. The inventive supercapacitor was prepared according to the procedure used in example 1.
Example 9
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.005% of Carbon Nano Tube (CNT), 0.005% of Carbon Nano Fiber (CNF) or Graphene (Graphene), 1% of carbon black, 1% of Styrene Butadiene Rubber (SBR) binder and 92.99% of graphite; 5% reduced graphene oxide dispersion. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 10
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 4.5% of Carbon Nanofiber (CNF), 4.5% of Carbon Nanotube (CNT) or Graphene (Graphene), 18% of acetylene black, 18% of butadiene rubber (BDR) binder, 13% of lithium iron phosphate, 12% of lithium cobaltate and 20% of ternary NCM; a 10% reduced graphene oxide dispersion. A lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 11
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 2% of Carbon Nano Tube (CNT), 2.5% of Graphene (Graphene), 6% of carbon black, 2.5% of conductive graphite, 4% of polyvinyl alcohol (PVA), 5% of polyvinylidene fluoride (PVDF) binder, 16% of lithium manganate, 15% of lithium nickel manganate, 20% of lithium cobaltate and 22% of ternary NCA; 5% graphene oxide dispersion. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 12
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 1% of Carbon Nanofiber (CNF), 2% of Carbon Nanotube (CNT), 3% of carbon black, 4% of conductive carbon fiber, 3% of acetylene black, 4% of polyvinylidene fluoride (PVDF), 4% of Polytetrafluoroethylene (PTFE), 4% of polyvinyl alcohol (PVA), 15% of graphite, 17% of silicon, 15% of silicon/carbon composite material and 18% of lithium titanate; 10% graphene oxide dispersion. A lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 13
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.5% of Graphene (Graphene), 0.5% of Carbon Nanofiber (CNF), 1.5% of Carbon Nano Tube (CNT), 1.5% of carbon black, 2.5% of conductive graphite, 3.5% of conductive carbon fiber, 3% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 3% of sodium carboxymethyl cellulose (CMC), 4% of polyvinyl alcohol (PVA), 6% of acrylic acid resin (AAP), 12% of lithium cobaltate, 35% of lithium manganate and 22% of ternary NCA. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 14
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.8% of Graphene (Graphene), 0.2% of Carbon Nanofiber (CNF), 1.0% of Carbon Nanotube (CNT), 1.0% of carbon black, 1.0% of conductive graphite, 1.5% of conductive carbon fiber, 1.5% of acetylene black, 1% of polyvinylidene fluoride (PVDF), 3% of Polytetrafluoroethylene (PTFE), 2% of sodium carboxymethylcellulose (CMC), 1% of polyvinyl alcohol (PVA), 2% of acrylic resin (AAP), 33.99% of lithium iron phosphate, 17% of lithium cobaltate, 15% of lithium manganate and 18% of lithium nickel manganate; 0.01% reduced graphene oxide dispersion. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 15
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.8% of Graphene (Graphene), 0.2% of Carbon Nanofiber (CNF), 1.0% of Carbon Nanotube (CNT), 1.0% of carbon black, 1.0% of conductive graphite, 1.5% of conductive carbon fiber, 1.5% of acetylene black, 1% of polyvinylidene fluoride (PVDF), 3% of Polytetrafluoroethylene (PTFE), 2% of sodium carboxymethylcellulose (CMC), 1% of polyvinyl alcohol (PVA), 1.99% of acrylic acid resin (AAP), 20% of soft carbon, 20% of graphite, 15% of mesocarbon microsphere, 15% of silicon/carbon composite material and 14% of silicon; 0.01% graphene oxide dispersion, the lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 16
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 0.5% of Graphene (Graphene), 0.5% of Carbon Nanofiber (CNF), 1.5% of Carbon Nanotube (CNT), 1.5% of carbon black, 2.5% of conductive graphite, 3.5% of conductive carbon fiber, 3% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 3% of sodium carboxymethyl cellulose (CMC), 4% of polyvinyl alcohol (PVA), 6% of acrylic acid resin (AAP) and 69% of Graphene in-situ coated lithium ion battery electrode material. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Example 17
The three-dimensional nano composite electrode material comprises the following components in percentage by mass: 1% of Carbon Nanofiber (CNF), 2% of Carbon Nanotube (CNT), 3% of carbon black, 5% of conductive carbon fiber, 4% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 5% of Polytetrafluoroethylene (PTFE), 5% of polyvinyl alcohol (PVA) and 70% of graphene in-situ coated lithium ion battery electrode material. The lithium ion battery of the invention was prepared according to the procedure used in example 2.
Comparative experiment example 1
Preparation and test of conventional activated carbon electrode for supercapacitor
1. Preparation of conventional activated carbon electrode for super capacitor
1.1 preparation of conventional energy-type activated carbon electrode (AC/SP/SBR/CMC = 90/5/3/2)
1.1.1 preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) Mixed solution
A uniformly dispersed mixed solution of CMC and SBR was prepared in the same manner as in 1.1 step A of example 1, and 7 g of ultrapure water was added to adjust the solid content of the solution.
1.1.2 preparation of conventional energy-type activated carbon electrode (AC/SP/SBR/CMC = 90/5/3/2) slurry
Accurately weighing 5 wt% (0.3 g) of conductive agent SP, adding the conductive agent SP into the mixed solution of CMC and SBR prepared in the step 1.1.1, setting the rotating speed of a vacuum stirrer to be 500 r/min, stirring at room temperature for 60 min, then accurately weighing 90 wt% (5.4 g) of AC solid powder, adding the AC solid powder into the mixed solution by three times, setting the rotating speed of the vacuum stirrer to be 500 r/min, stirring at room temperature for 30 min each time, and preparing the conventional energy type active carbon electrode slurry.
1.1.3 preparation of conventional energy-type activated carbon electrode (AC/SP/SBR/CMC = 90/5/3/2)
And (2) vacuumizing and standing the conventional energy type activated carbon electrode slurry prepared in the step (1.1.2) for 10 min, filtering the slurry by using a 100-mesh sieve, coating the slurry on a corroded aluminum foil current collector, drying the slurry at 60 ℃ for 3 h, rolling the dried slurry, punching the composite electrode into a circular pole piece with the diameter of 12 mm by using a slicing machine, and then drying the pole piece at 60 ℃ for 12 h in a vacuum manner to prepare the conventional energy type activated carbon electrode for the supercapacitor (AC/SP/SBR/CMC = 90/5/3/2) (as shown in a figure 2-a).
1.2 preparation of conventional Power-type activated carbon electrode (AC/SP/SBR/CMC = 80/10/7/3)
1.2.1 preparation of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) Mixed solution
A uniformly dispersed CMC and SBR mixed solution was prepared as in example 1, step A, 1.3.
1.2.2 preparation of conventional Power-type activated carbon (AC/SP/SBR/CMC = 80/10/7/3) electrode slurry
Accurately weighing 10 wt% (0.6 g) of conductive agent SP, adding into the mixed solution of CMC and SBR prepared in the step 1.2.1, setting the rotating speed of a vacuum stirrer to be 500 r/min, and stirring at room temperature for 60 min; then, AC solid powder with the mass ratio of 80 wt% (4.8 g) is accurately weighed and added into the mixed solution for three times, the rotating speed of a vacuum stirrer is set to be 500 r/min, and the mixture is stirred at room temperature for 30 min each time, so that the conventional power type active carbon electrode slurry is prepared.
1.2.3 preparation of conventional Power-type activated carbon electrode (AC/SP/SBR/CMC = 80/10/7/3)
And (3) vacuumizing and standing the conventional power type activated carbon electrode slurry prepared in the step (1.2.2) for 10 min, filtering the slurry by using a 100-mesh sieve, coating the slurry on a corroded aluminum foil current collector, drying the slurry at the temperature of 60 ℃ for 3 h, rolling the dried slurry, punching the slurry into a circular pole piece with the diameter of 12 mm by using a slicing machine, and drying the pole piece at the temperature of 60 ℃ for 12 h in a vacuum manner to prepare the conventional power type activated carbon electrode for the supercapacitor (AC/SP/SBR/CMC = 80/10/7/3) (as shown in a figure 2-b).
Conventional activated carbon electrode test for supercapacitor
2.1 high power Scanning Electron Microscope (SEM) testing
The conventional energy type activated carbon electrode (AC/SP/SBR/CMC = 90/5/3/2) and the conventional power type activated carbon electrode (AC/SP/SBR/CMC = 80/10/7/3) for the supercapacitor prepared from the above comparative experimental example 1 were subjected to characterization tests of morphological characteristics using a high power Scanning Electron Microscope (SEM). The test result shows that: in the conventional activated carbon electrode, the conductive network is formed completely by the agglomeration of conductive agent SP particles, and the contact between the SP particle agglomerates and AC particles is poor (as shown in figures 2-a and 2-b), so that the conductive network with high conductivity cannot be formed.
2.2 electrochemical performance test:
2.2.1 encapsulation
In the control of oxygen (A)<0.1 ppm) and water (C)<0.1 ppm) was charged into a glove box, a conventional activated carbon electrode for a supercapacitor of comparative experimental example 1, a LIR2025 battery case, a cellulose acetate separator, and 1M [ TEA ]][BF 4 ]The button type super capacitor is assembled by the ACN electrolyte, and is used for electrochemical performance test after standing for 1 hour at room temperature.
2.2.2 electrochemical Performance test
a. And (3) testing alternating current impedance: and (3) carrying out an alternating current impedance test on the button type super capacitor packaged in the step 2.2.1 at an open circuit voltage by adopting an alternating current amplitude of 10 mV within a frequency range of 100 kHz-10 mHz (as shown in attached figures 3 and 4). Test results show that the conductive network of the conventional activated carbon electrode is formed by only SP particle aggregates, so that the electrode has relatively high charge transfer resistance and diffusion resistance and poor conductivity.
b. And (3) rate testing: the button-type super capacitor packaged in the step 2.2.1 is in the voltage range of 0-2.7VIn the enclosure, 0.5-80A g is adopted -1 The current density of (a) was tested for rate capability (as shown in fig. 5 and 6). The test result shows that: because the conductive network of the conventional activated carbon electrode is only composed of the SP particle aggregate, and the SP particle aggregate and the AC particles have poor contact and poor conductivity, the rate capability of the two conventional activated carbon electrodes is relatively poor. At 80 ag -1 The capacity retention ratio of the conventional energy type activated carbon electrode is only 55.29% (figure 5), and the capacity retention ratio of the conventional power type activated carbon electrode is only 54.51% (figure 6).
c. Cyclic voltammetry testing: the button-type super capacitor packaged in the step 2.2.1 is within the voltage range of 0-2.7V by adopting 500 mV S -1 The sweep rate of (a) was used to perform cyclic voltammetry tests (as shown in FIGS. 7 and 8). The test result shows that: as the conductive network of the conventional activated carbon electrode is only formed by SP particle aggregates and has poor conductivity, the voltammetry curve of the electrode is 500 mV S -1 The large scanning speed of (2) seriously deviates from the rectangle, and the quick response characteristic is poor.
d. And (3) testing the cycle life: the voltage of the button type super capacitor packaged in the step 2.2.1 is in the range of 0-2.7V, and 10 Ag is adopted -1 The current density of (a) was subjected to a cycle life test (as shown in fig. 9 and 10). The test result shows that: because the conductive network of the conventional activated carbon electrode is only formed by SP particle aggregates, the electrode has poor conductivity and rate capability, and the electrode shows poor cycling stability. At 10 ag -1 The capacity retention ratio of the conventional energy type activated carbon electrode after 30000 cycles is only 69.54% (shown in figure 9), and the capacity retention ratio of the conventional power type activated carbon electrode after 15000 cycles is only 82.47% (shown in figure 10).
Comparative experiment example 2
Preparation and testing of conventional lithium iron phosphate electrodes for lithium ion batteries (LFP/SP/KS 6/PVDF = 92/3/1/4)
1. Preparation of conventional lithium iron phosphate electrode for lithium ion battery (LFP/SP/KS 6/PVDF = 92/3/1/4)
1.1.1 preparation of conventional lithium iron phosphate electrode slurry for lithium ion batteries
Adding 30 mL of NMP into a 50 mL stirring tank, weighing PVDF solid with the mass ratio of 4 wt% (0.8 g) and adding the PVDF solid into the NMP solution, stirring for 90 min to completely dissolve the PVDF, adding a conductive agent SP with the mass ratio of 3 wt% (0.6 g) and a conductive agent KS6 with the mass ratio of 1 wt% (0.2 g) and stirring for 90 min to uniformly disperse the conductive agents, weighing LFP material with the mass ratio of 92 wt% (18.4 g) and adding the LFP material into the solution four times, and stirring for 30 min each time to prepare the conventional lithium iron phosphate electrode slurry for the lithium ion battery.
1.1.2 preparation of conventional lithium iron phosphate electrode for lithium ion battery
The electrode slurry was used to prepare an electrode by the method of step D1.1 in example 2, and a conventional lithium iron phosphate electrode for lithium ion batteries (LFP/SP/KS 6/PVDF = 92/3/1/4) was prepared (as shown in fig. 11-D).
2. Testing of conventional lithium iron phosphate electrodes for lithium ion batteries (LFP/SP/KS 6/PVDF = 92/3/1/4)
2.1 high power Scanning Electron Microscope (SEM) testing
The lithium ion battery prepared from the above comparative experimental example 2 was subjected to characterization test of morphological characteristics using a high power Scanning Electron Microscope (SEM) using a conventional lithium iron phosphate electrode (LFP/SP/KS 6/PVDF = 92/3/1/4) (as shown in fig. 11-d). The test result shows that: in the conventional lithium iron phosphate electrode, a conductive network is completely formed by conductive agent SP and KS6 particles, and the SP and KS6 are in poor contact with LFP particles, so that an efficient conductive network cannot be formed.
2.2 electrochemical Performance testing
2.2.1 encapsulation
In the control of oxygen (<0.1 ppm) and water (C)<0.1 ppm), a conventional lithium iron phosphate electrode (LFP/SP/KS 6/PVDF = 92/3/1/4) for a lithium ion battery prepared by comparative experimental example 2 (as a positive electrode), a lithium sheet (as a negative electrode), a LIR2025 battery case, a PP/PE/PP separator, and 1M LiPF were used in a glove box 6 The electrolyte of the EC-EMC-DMC (volume ratio 1.
2.2.2 electrochemical Performance test
a. And (3) testing alternating current impedance: and (3) carrying out an alternating current impedance test on the button lithium ion battery packaged in the step 2.2.1 under the open circuit voltage by adopting the alternating current amplitude of 10 mV within the frequency range of 100 kHz-1 mHz (as shown in figure 12). Test results show that in a conventional lithium iron phosphate electrode, a conductive network is completely formed by conductive agents SP and KS6, and the SP and KS6 are in poor contact with LFP particles, so that an efficient conductive network cannot be formed, and the electrode is large in charge transfer resistance and poor in conductivity.
b. And (3) multiplying power testing: and (3) charging the button lithium ion battery packaged in the step 2.2.1 at 0.2C in a voltage range of 2-4V at room temperature, respectively performing discharge tests of different multiplying powers of 0.2C, 1C, 2C, 3C, 5C, 7C, 10C and the like, and circulating for 5 times at each multiplying power (as shown in figure 13). The test result shows that: since the conductive network in the conventional lithium iron phosphate electrode is completely formed by the conductive agents SP and KS6, and the SP and KS6 are in poor contact with the LFP particles, a high-efficiency conductive network cannot be formed, the discharge specific capacity of the conventional lithium iron phosphate electrode prepared by the comparative experimental example 2 at the current density of 1C is only 128.1 mAh g -1 And the capacity retention rate at a large current density of 7C was only 25% (as shown in fig. 13), showing poor rate characteristics.
Comparative analysis
The invention carries out composite modification on a porous carbon electrode material for a supercapacitor or a lithium ion battery electrode material by introducing two or more than two nano carbon materials and a conductive agent. In the obtained novel three-dimensional nano composite electrode material for the super capacitor or the lithium ion battery, the nano carbon material is uniformly wound (coated) on the surface of the porous carbon material particles (figure 1) or the surface of the lithium ion battery electrode material particles (figures 11-a,11-b and 11-c), and is connected with the conventional conductive agent particles to jointly form a good three-dimensional conductive network. Compared with the conventional electrode material for the supercapacitor (shown in figure 2) or the conventional electrode material for the lithium ion battery (shown in figure 11-d) which is not subjected to nano-carbon material composite modification, the nano-carbon material composite modification technology can fully exert the synergistic effect of a plurality of nano-carbon materials and conventional conductive agents, and greatly improve the conductivity (shown in figures 3 and 4) and rate capability (shown in figures 5 and 6) of the porous carbon electrode for the supercapacitor or the conductivity (shown in figure 12) and rate capability (shown in figure 13) of the electrode material for the lithium ion battery, so that the power characteristics, the power density and the cycle service life (shown in figures 9 and 10) of the supercapacitor or the lithium ion battery based on the high-performance novel three-dimensional nano-composite electrode material are greatly improved.
In addition, the invention carries out composite modification on the porous carbon electrode material for the supercapacitor or the lithium ion battery electrode material by introducing two or more nano carbon materials and a conductive agent. The synergistic effect and the shape effect of the nano-carbon material and the conventional conductive agent are fully exerted, and the carbon nano-tube and the graphene are uniformly wound (coated) on the surface of the porous carbon electrode material or the lithium ion battery electrode material for the supercapacitor; the carbon nano tubes and the carbon nano fibers are connected among particles of a porous carbon electrode material or a lithium ion battery electrode material for the supercapacitor; the conventional conductive agent particles are effectively filled among particles of a porous carbon electrode material or a lithium ion battery electrode material for a supercapacitor, so that the three-dimensional nano composite electrode material disclosed by the invention is more compact and has high assembly density, and the energy density of the supercapacitor or the lithium ion battery based on the high-performance novel three-dimensional nano composite electrode material disclosed by the invention is improved.
In conclusion, the three-dimensional nano composite electrode material for electrochemical energy storage has high assembly density, good conductivity, rate characteristic and excellent electrochemical stability, and the preparation method of the three-dimensional nano composite electrode material for electrochemical energy storage has the advantages of simple process, environmental protection, low cost and suitability for industrial production.

Claims (2)

1. The supercapacitor composite electrode is characterized in that the three-dimensional nano composite electrode material consists of 0.5% of carbon nanofiber CNF, 1.5% of carbon nanotube CNT, 1.5% of carbon black, 2.5% of conductive graphite, 3.5% of conductive carbon fiber, 3% of acetylene black, 5% of polyvinylidene fluoride (PVDF), 3% of sodium carboxymethylcellulose (CMC), 4% of polyvinyl alcohol (PVA), 6% of acrylic resin (AAP) and 69.5% of porous carbon composite material coated with reduced graphene oxide in situ in percentage by mass;
the preparation method of the supercapacitor composite electrode comprises the steps of graphite oxide preparation, reduced graphene oxide in-situ coated porous carbon composite material preparation, carbon nanofiber dispersion liquid preparation and composite electrode preparation, and specifically comprises the following steps:
A. preparing graphite oxide: according to an improved Hummers method, oxidizing flake graphite with a certain mass by potassium permanganate with a mass ratio of 3 to the flake graphite and concentrated sulfuric acid with a volume/mass ratio of 23 ml/1g, reducing by hydrogen peroxide to remove residual oxidant, separating, washing and drying to prepare a graphite oxide solid;
B. preparing a reduced graphene oxide in-situ coated porous carbon composite material: b, adding the graphite oxide prepared in the step A, a porous carbon material and a reducing agent hydrazine hydrate into an aqueous solution for ultrasonic stripping and reduction to form reduced graphene oxide, simultaneously carrying out in-situ coating on the porous carbon material, and separating, washing and drying to prepare a reduced graphene oxide in-situ coated porous carbon composite material;
C. preparing a carbon nanofiber dispersion liquid: acidizing the carbon nanofibers by using mixed acid of concentrated sulfuric acid/concentrated nitric acid, adding a surfactant to ultrasonically disperse the obtained acidized carbon nanofibers in an aqueous solution, and preparing a carbon nanofiber dispersion solution;
D. preparing a composite electrode: according to the mass ratio, adding 69.5% of the reduced graphene oxide in-situ coated porous carbon composite material prepared in the step B, 1.5% of carbon nano tube CNT, 1.5% of carbon black, 2.5% of conductive graphite, 3.5% of conductive carbon fiber, 3% of acetylene black, 5% of polyvinylidene fluoride PVDF, 3% of sodium carboxymethyl cellulose CMC, 4% of polyvinyl alcohol PVA, 6% of acrylic resin AAP and 0.5% of carbon nano fiber dispersion liquid CNF prepared in the step C into an aqueous solution together, forming electrode slurry after vacuum high-speed stirring, then uniformly coating the electrode slurry on the surface of a current collector, and preparing the three-dimensional nano composite electrode of the super capacitor after drying, rolling and slitting;
the three-dimensional nano composite electrode has high assembly density, good conductivity, excellent rate characteristic and excellent electrochemical stability;
the porous carbon composite material coated with the reduced graphene oxide in situ specifically comprises 0.5% of reduced graphene oxide, 12% of activated carbon cloth, 35% of activated carbon fiber and 22% of porous hard carbon.
2. The supercapacitor composite electrode is characterized in that the three-dimensional nano composite electrode material consists of 0.2% of carbon nanofiber CNF, 1.0% of carbon nanotube CNT, 1.0% of carbon black, 1.0% of conductive graphite, 1.5% of conductive carbon fiber, 1.5% of acetylene black, 1% of polyvinylidene fluoride PVDF, 3% of polytetrafluoroethylene PTFE, 2% of sodium carboxymethyl cellulose CMC, 1% of polyvinyl alcohol PVA, 2% of acrylic resin AAP and 84.8% of porous carbon composite material coated with reduced graphene oxide in situ in percentage by mass;
the preparation method of the supercapacitor composite electrode comprises the steps of graphite oxide preparation, reduced graphene oxide in-situ coated porous carbon composite material preparation, carbon nanofiber dispersion liquid preparation and composite electrode preparation, and specifically comprises the following steps:
A. preparing graphite oxide: according to an improved Hummers method, potassium permanganate with a mass ratio of 3 to crystalline flake graphite and concentrated sulfuric acid with a volume/mass ratio of 23 ml/1g are used for oxidizing crystalline flake graphite with a certain mass, residual oxidant is removed by reduction with hydrogen peroxide, and a graphite oxide solid is prepared by separation, washing and drying;
B. preparing a reduced graphene oxide in-situ coated porous carbon composite material: b, adding the graphite oxide prepared in the step A, a porous carbon material and a reducing agent hydrazine hydrate into an aqueous solution for ultrasonic stripping and reduction to form reduced graphene oxide, simultaneously carrying out in-situ coating on the porous carbon material, and separating, washing and drying to prepare a reduced graphene oxide in-situ coated porous carbon composite material;
C. preparing a carbon nanofiber dispersion liquid: acidizing carbon nanofibers by using mixed acid of concentrated sulfuric acid/concentrated nitric acid, adding a surfactant to ultrasonically disperse the obtained acidized carbon nanofibers in an aqueous solution, and preparing a carbon nanofiber dispersion solution;
D. preparing a composite electrode: adding 84.8% of the reduced graphene oxide in-situ coated porous carbon composite material prepared in the step B, 1.0% of carbon nanotube CNT, 1.0% of carbon black, 1.0% of conductive graphite, 1.5% of conductive carbon fiber, 1.5% of acetylene black, 1% of polyvinylidene fluoride PVDF, 3% of polytetrafluoroethylene PTFE, 2% of sodium carboxymethyl cellulose CMC, 1% of polyvinyl alcohol PVA, 2% of acrylic resin AAP and 0.2% of carbon nanofiber dispersion liquid CNF prepared in the step C into an aqueous solution together according to the mass ratio, stirring at a high speed in vacuum to form electrode slurry, uniformly coating the electrode slurry on the surface of a current collector, and drying, rolling and cutting to prepare the three-dimensional nano composite electrode of the supercapacitor;
the three-dimensional nano composite electrode has high assembly density, good conductivity, excellent rate characteristic and excellent electrochemical stability;
the porous carbon composite material coated with the reduced graphene oxide in situ specifically comprises 0.8% of the reduced graphene oxide, 15% of activated carbon powder, 18% of activated carbon cloth, 28% of activated carbon fiber, 12% of porous graphite and 11% of carbon aerogel.
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