CN110415994A - A kind of electrochemical energy storage three-dimensional manometer combination electrode material and preparation method thereof - Google Patents
A kind of electrochemical energy storage three-dimensional manometer combination electrode material and preparation method thereof Download PDFInfo
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- CN110415994A CN110415994A CN201910664209.0A CN201910664209A CN110415994A CN 110415994 A CN110415994 A CN 110415994A CN 201910664209 A CN201910664209 A CN 201910664209A CN 110415994 A CN110415994 A CN 110415994A
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- electrode material
- lithium ion
- graphene
- dimensional manometer
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Classifications
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- B82—NANOTECHNOLOGY
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- 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
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- H01G11/32—Carbon-based
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- H—ELECTRICITY
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- 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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- H01M10/00—Secondary cells; Manufacture thereof
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/04—Processes of manufacture in general
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention discloses a kind of electrochemical energy storage three-dimensional manometer combination electrode materials and preparation method thereof.Electrochemical energy storage three-dimensional manometer combination electrode material, is combined by two or more nano-carbon material, conductive agent, binder and electrode material for super capacitor or lithium ion battery electrode material.The preparation method of electrochemical energy storage three-dimensional manometer combination electrode material, including supercapacitor is prepared with three-dimensional manometer combination electrode and prepared by lithium ion battery three-dimensional manometer combination electrode.Present invention introduces two or more nano-carbon material and conductive agent are composite modified to supercapacitor or lithium ion battery electrode material progress; pass through the optimization to complex method; give full play to a variety of nano-carbon materials and its synergistic effect with conductive agent; so that three-dimensional manometer combination electrode material packing density height of the invention, good conductivity, multiplying power property and electrochemical stability are excellent, and preparation process it is simple, it is environmentally protective, low in cost, be suitable for large-scale production.
Description
Technical field
The present invention relates to electrochemical energy technical field of memory, in particular to a kind of supercapacitor or lithium ion battery are used
High-performance novel three-dimensional manometer combination electrode material and preparation method thereof.
Background technique
Since 20th century, economy rapid development, resource is on the verge of exhaustion, and pollution is on the rise, searching can replace petroleum,
The novel renewable energy of the fossil energies such as coal, natural gas is extremely urgent.At the same time, the high speed development of new energy source technology
Bring the urgent need to novel energy-storing technology.
Supercapacitor (also referred to as electrochemical capacitor) be in recent decades both at home and abroad it is emerging grow up it is a kind of between
Conventional capacitor and chemical cell novel energy-storing element between the two.Due to its power density (10 with higher3~104 W
kg-1), the special performances such as the cycle life of overlength (up to hundreds of thousands of times) and wider operating temperature range (- 40~70 DEG C),
Supercapacitor has been widely used in the fields such as communications and transportation, renewable energy, industry and consumption electronic product.It is commercial at present
The electrode material of supercapacitor is mainly high specific surface area porous carbon material, such as active carbon (AC) powder, active carbon cloth, active carbon
Fiber, carbon aerogels, porous graphite, porous hard carbon, mesoporous carbon etc., such porous carbon materials due to preparation process is more mature,
The advantages that abundant raw materials, lower production costs, has been used as the mainstream electrode material of supercapacitor.As market is to super
The continuous improvement that capacitor performance requires, such porous carbon materials electric conductivity is poor, packing density is low, cyclical stability is poor etc. no
Foot is increasingly prominent, leads to that the capacitor energy density based on such porous carbon electrode material is low, power-performance is poor, service life
It is limited.In addition, the conductive agent used in commercialization electrode material for super capacitor preparation process at present is mainly conductive black
(such as: SP), electric conductivity has certain limitation, causes the electrode material electric conductivity thus prepared relatively poor.Therefore,
How to improve the packing density of supercapacitor porous carbon electrodes, improve its electric conductivity, prepares with high conductivity, high group
Fill density, the electrode for super capacitor material of high circulation stability becomes technical problem in the urgent need to address.
In recent years, with nano-carbon material (graphene (Graphene), carbon nanotube (CNT), carbon nano-fiber (CNF)
Deng) rise, the advantages that excellent physical and chemical performance, splendid electric conductivity, structure nano becomes new material neck
The research hotspot in domain, a large amount of research work are dedicated to pure nano-carbon material being used as electrode material for super capacitor
(CN106653389A, CN101271969A etc.).However, the extremely low packing density of nano-carbon material, complicated preparation process and
High production cost makes it be difficult to carry out scale, commercial applications.To which nano-carbon material is used as conductive additive
It combines, carries out composite modified and preparing the research of novel nano carbon-porous carbon composite electrode becomes super with porous carbon materials
The hot subject of capacitor electrode material field in recent years.Such as CN106847834A, CN102214515A, CN1942985A are special
Benefit, which is individually disclosed, prepares combination electrode for the nano-carbon materials such as absorbent charcoal material and graphene, carbon nanotube, carbon nano-fiber
Method, the performance of the combination electrode material prepared by these methods is improved, but such by single nano-carbon material and more
The carbon electrode composite modified method to improve combination electrode performance in hole has limitation, and it is super for high-performance to be still difficult to meet market
The requirement of grade capacitor.
Compared with supercapacitor, lithium ion battery alternatively emerging energy-storage travelling wave tube has relatively higher
It is widely applied in fields such as rail vehicle transportation, new-energy automobiles in operating voltage and energy density.But due to lithium-ion electric
The charge and discharge process of pond electrode material relates generally to reversible insertion/deintercalation of lithium ion, so that the power-performance of lithium ion battery
With service life it is significant be lower than supercapacitor, and the key for improving lithium ion battery power characteristic and service life is to mention
The electric conductivity and cyclical stability of high-lithium ion battery electrode material.Common anode material for lithium-ion batteries mainly has: phosphorus
Sour iron lithium (LFP), cobalt acid lithium (LCO), LiMn2O4 (LMO), nickel ion doped (LNMO), ternary material (NCM, NCA) etc., cathode material
Material mainly has: graphite, hard carbon, soft carbon, mesocarbon microspheres, silicon, silicon/carbon composite, lithium titanate (LTO) etc..Currently, business
Change the conductive agent that uses in lithium ion battery electrode material preparation process be mainly conductive black (such as: SP) and electrically conductive graphite (such as:
KS6), electric conductivity is significantly below nano-carbon material, causes the electrode material electric conductivity thus prepared relatively poor.Therefore,
Nano-carbon material is used as conductive additive and lithium ion battery electrode material progress is composite modified, improves the conduction of combination electrode
Performance and then the power characteristic for improving lithium ion battery, have higher feasibility study and larger market application potential.Based on this, specially
Sharp CN105047874A, CN102569796A individually disclose LiFePO 4 material and graphene, carbon nanotube are carried out it is compound
The modified method for preparing combination electrode, patent CN107706397A, CN101764219A individually disclose ternary material, graphite material
Material carries out the composite modified method for preparing combination electrode with carbon nanotube, is answered by lithium ion cell nano carbon prepared by this class method
The high rate performance of composite electrode material is to a certain degree of improvement, but such by single nano-carbon material and lithium ion cell electrode
The modified method to improve lithium ion battery power-performance of Material cladding has limitation, is still difficult to meet market for Gao Gong
The requirement of rate, long circulating, lithium ion battery with high energy density, especially new-energy automobile field is to high-energy density, high power
The rigors of characteristic and long circulation life lithium-ion-power cell.
Summary of the invention
An object of the present disclosure is to provide a kind of packing density height, good conductivity, multiplying power property and electrochemical stability
Excellent electrochemical energy storage three-dimensional manometer combination electrode material；Second be designed to provide a kind of preparation process it is simple,
The supercapacitor of electrochemical energy storage three-dimensional manometer combination electrode material low in cost, suitable for large-scale production is three-dimensional
Nanometer combined electrode preparation method；Third is designed to provide a kind of electrochemical energy storage three-dimensional manometer combination electrode material
Lithium ion three-dimensional manometer method for preparing composite electrode.
The first object of the present invention is achieved in that by two or more nano-carbon material, conductive agent, binder
The three-dimensional manometer combination electrode material is combined with supercapacitor porous carbon electrode material or lithium ion battery electrode material
Material.
The second object of the present invention is achieved in that the supercapacitor of the three-dimensional manometer combination electrode material is three-dimensional
Nanometer combined electrode preparation method, including graphite oxide preparation, the preparation of graphene in-stiu coating porous carbon materials, carbon nano-fiber
Dispersion liquid preparation, supercapacitor three-dimensional manometer combination electrode preparation step, it is characterised in that specifically include:
A, prepared by graphite oxide: referring to improved Hummers method, with the potassium permanganate and body for being 3:1 with crystalline flake graphite mass ratio
Product/mass ratio is that the concentrated sulfuric acid of 23 ml:1 g aoxidizes the crystalline flake graphite of certain mass, is removed with hydrogen-peroxide reduction surplus
Remaining oxidant, separating, washing, drying, is prepared oxidation graphite solid；
B, graphene in-stiu coating porous carbon materials prepare: the graphite oxide that the step A is prepared in aqueous solution into
Row ultrasound 3~5 h of removing, form graphene oxide and carry out in-stiu coating to porous carbon simultaneously, then with hydrazine hydrate to gained oxygen
Graphite alkene is restored, and the porous carbon materials of redox graphene in-stiu coating are prepared in separating, washing, drying；
C, prepared by carbon nanofiber dispersion liquid: the concentrated sulfuric acid/concentrated nitric acid mixed acid for being 3:1~5:1 with volume ratio is to carbon nanometer
Fiber is acidified, and the surfactant that 4~20 mM/L are added is acidified carbon nano-fiber ultrasonic disperse in aqueous solution to gained
30~120 min, are prepared carbon nanofiber dispersion liquid；
D, prepared by supercapacitor three-dimensional manometer combination electrode: in mass ratio by 50~97.99% porous carbon electrode materials, 0.01
~10% nano-carbon material, 1~20% conductive agent, 1~20% binder and 0.01~10% step C made from carbon nano-fiber point
Dispersion liquid；Or redox graphene in-stiu coating porous carbon materials made from the step B in mass ratio by 50~97.99%, 1~
20% conductive agent, 1~20% binder and 0.01~10% step C made from carbon nanofiber dispersion liquid or 0.01~10% nanometer
Carbon material is added in aqueous solution together, forms electrode slurry after vacuum high-speed stirred, is then uniformly coated on electrode slurry
On collection liquid surface, supercapacitor three-dimensional manometer combination electrode is made after drying, roll-in, cutting.
The surfactant is lauryl sodium sulfate, neopelex, dodecyl sodium sulfate or poly-
One of vinylpyrrolidone or more than one；The aqueous solution is ultrapure water, deionized water or distilled water.
The third object of the present invention is achieved in that the lithium ion battery of the three-dimensional manometer combination electrode material is three-dimensional
Nanometer combined electrode preparation method, including the preparation of graphene in-stiu coating lithium ion battery electrode material, graphene oxide dispersion
Liquid preparation, the preparation of redox graphene dispersion liquid, lithium ion battery three-dimensional manometer combination electrode preparation step, it is characterised in that
It specifically includes:
A, prepared by graphene in-stiu coating lithium ion battery electrode material: graphite oxide is carried out to ultrasound removing 3 in ultrapure water
~4 h, gained graphene oxide is restored with hydrazine hydrate and in-stiu coating, warp are carried out to lithium ion battery electrode material
Separation, washing, drying, are prepared redox graphene in-stiu coating lithium ion battery electrode material；
B, prepared by graphene oxide dispersion: the graphite oxide is carried out to ultrasonic removing, dispersion in N-Methyl pyrrolidone,
Graphene oxide dispersion is prepared；
C, prepared by redox graphene dispersion liquid: graphite oxide is subjected to high temperature reduction under the atmosphere of nitrogen or argon gas, with
N-Methyl pyrrolidone is solution, carries out ultrasound 60~120 min of removing to resulting redox graphene and disperses, prepares
Obtain redox graphene dispersion liquid；
D, lithium ion battery three-dimensional manometer combination electrode prepare: in mass ratio by 50~97.99% lithium ion battery electrode materials,
0.01~10% nano-carbon material, 1~20% conductive agent, 1~20% binder and 0.01~10% step B made from graphite oxide
Alkene dispersion liquid or 0.01~10% step C made from redox graphene dispersion liquid；Or in mass ratio by 50~97.99%
Graphene in-stiu coating lithium ion battery electrode material made from step A, 0.01~10% nano-carbon material, 1~20% conductive agent,
1~20% binder is added together in N-Methyl pyrrolidone solution, and electrode slurry is formed after vacuum high-speed stirred, then will
Electrode slurry is uniformly coated on collection liquid surface, and lithium ion battery three-dimensional manometer compound electric is made after drying, roll-in, cutting
Pole.
The present invention is based on polynary nanometer carbon complex systems, i.e., by introduce two or more nano-carbon material with lead
Electric agent carries out supercapacitor porous carbon electrode material or electrode material for lithium ion cell composite modified, gives full play to more
Kind nano-carbon material and its synergistic effect with conductive agent.It overcomes the prior art and compound electric is prepared using single nano-carbon material
The drawback that pole material packing density is low, high rate performance is poor and preparation process is complicated, supercapacitor of the invention and lithium-ion electric
Pond three-dimensional manometer combination electrode material has high assembled density, and good conductivity, multiplying power property and electrochemical stability are excellent
It is different.Based on supercapacitor or the lithium ion battery of the invention super electricity of high-performance novel three-dimensional manometer combination electrode material
Container and lithium ion battery have higher energy density, power density and a service life cycle, further satisfaction market for
The demand of high-energy density/high power density supercapacitor or lithium ion battery.Method preparation process of the invention is simple, green
Colour circle is protected, is low in cost, and industrialized production is suitable for, and is a kind of preparation supercapacitor or lithium ion for being easier to realize industrialization
The new method of battery high-performance novel three-dimensional manometer combination electrode material.
Detailed description of the invention
Fig. 1 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/CNT/CNF/SP/SBR/ prepared by embodiment 1
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)) high power scanning electron microscope (SEM) photograph
Picture.
Fig. 2 is the regular power type (2-a) prepared by comparative experiments example 1 and ordinary power type (2-b) activated carbon electrodes
High power scanning electron microscope image.
Fig. 3 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/CNT/CNF/SP/SBR/ prepared by embodiment 1
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 AC impedance figure of regular power type activated carbon electrodes prepared by comparative experiments example 1.
Fig. 4 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/rGO/CNF/SP/SBR/ prepared by embodiment 1
CMC(78.75/1.25/1.25/8.75/7/3)) and comparative experiments example 1 prepare ordinary power type activated carbon electrodes exchange
Impedance diagram.
Fig. 5 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/CNT/CNF/SP/SBR/ prepared by embodiment 1
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 curve of double curvature figure of regular power type activated carbon electrodes prepared by comparative experiments example 1.
Fig. 6 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/rGO/CNF/SP/SBR/ prepared by embodiment 1
CMC(78.75/1.25/1.25/8.75/7/3)) and comparative experiments example 1 prepare ordinary power type activated carbon electrodes multiplying power
Curve graph.
Fig. 7 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/CNT/CNF/SP/SBR/ prepared by embodiment 1
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 cyclic voltammetry curve figure of regular power type activated carbon electrodes prepared by comparative experiments example 1.
Fig. 8 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/rGO/CNF/SP/SBR/ prepared by embodiment 1
CMC(78.75/1.25/1.25/8.75/7/3)) and comparative experiments example 1 prepare ordinary power type activated carbon electrodes circulation
Volt-ampere curve figure.
Fig. 9 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/CNT/CNF/SP/SBR/ prepared by embodiment 1
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 cycle life curve figure of regular power type activated carbon electrodes prepared by comparative experiments example 1.
Figure 10 is the supercapacitor novel three-dimensional nanometer combined electrode (AC/rGO/CNF/SP/ prepared by embodiment 1
)) and the ordinary power type activated carbon electrodes that prepare of comparative experiments example 1 SBR/CMC(78.75/1.25/1.25/8.75/7/3
Cycle life curve figure.
Figure 11 be prepared by embodiment 2 lithium ion battery novel three-dimensional nanometer combined electrode (redox graphene/
Carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) combination electrode (LFP/rGO/CNT/SP/KS6/PVDF=90/1/1/3/1/4) (11-
A), graphene oxide/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) combination electrode (LFP/GO/CNT/SP/KS6/PVDF=90/
1/1/3/1/4) (11-b), redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) combination electrode (LFP/rGO/
CNT/SP/KS6/PVDF=90/1/1/3/1/4) (11-c)) and the lithium ion battery conventional phosphoric acid that is prepared by comparative experiments example 2
The high power scanning electron microscope (SEM) photograph image of iron lithium electrode (11-d).
Figure 12 is the lithium ion battery novel three-dimensional nanometer combined electrode prepared by embodiment 2 and comparative experiments example 2
The AC impedance comparative analysis figure of the lithium ion battery of preparation conventional phosphoric acid iron lithium electrode.
Figure 13 is the lithium ion battery novel three-dimensional nanometer combined electrode prepared by embodiment 2 and comparative experiments example 2
The curve of double curvature comparative analysis figure of the lithium ion battery of preparation conventional phosphoric acid iron lithium electrode.
Specific embodiment
Below in conjunction with attached drawing, the present invention is described in further detail with embodiment, and the present embodiment is with skill of the present invention
Implemented under premised on art scheme, give detailed embodiment, but the present invention is limited in any way, base
In present invention teach that made any changes and modifications, all belong to the scope of protection of the present invention.
A kind of electrochemical energy storage three-dimensional manometer combination electrode material of the invention, by two or more nanometer
Carbon material, conductive agent, binder and supercapacitor porous carbon electrode material or lithium ion battery electrode material are combined institute
State three-dimensional manometer combination electrode material.
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: nano-carbon material 0.01~
10%, conductive agent 1~20%, binder 1~20%, supercapacitor porous carbon electrode material 50~97.99% or lithium ion battery
Electrode material 50~97.99%.
The nano-carbon material is carbon nanotube (CNT), graphene (Graphene), two in carbon nano-fiber (CNF)
Kind is two or more；The carbon nanotube is single-walled carbon nanotube and/or multi-walled carbon nanotube, and the graphene is mono-layer graphite
Alkene and/or multi-layer graphene.
The conductive agent is one of carbon black, acetylene black, electrically conductive graphite, conductive Carbon fibe or more than one combinations；Institute
Stating binder is sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), butadiene rubber (BDR), polyvinylidene fluoride
(PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), in acroleic acid resin (AAP) one or more kinds of combinations.
The supercapacitor porous carbon electrode material be active powdered carbon, active carbon cloth, activated carbon fibre, carbon aerogels,
One of porous graphite, porous hard carbon, mesoporous carbon or more than one combinations.
The positive electrode of the lithium ion battery electrode material is LiFePO4 (LFP), cobalt acid lithium (LCO), LiMn2O4
(LMO), one of nickel ion doped (LNMO) or ternary material (NCM, NCA) or more than one combinations；Negative electrode material be stone
One of ink, hard carbon, soft carbon, mesocarbon microspheres, silicon, silicon/carbon composite, lithium titanate (LTO) or more than one combinations.
The electrode material form is button wafer type, and column type is winding-type, stacked square or stacked abnormal shape.
Embodiment 1, the preparation and test of supercapacitor of the present invention high-performance novel three-dimensional manometer combination electrode:
1, the preparation of supercapacitor of the present invention high-performance novel three-dimensional manometer combination electrode
1.1 AC/CNT/CNF/SP/SBR/CMC(90/3.125/0.625/1.25/3/2) three-dimensional manometer combination electrode preparation
A, the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
It accurately weighs 1 g sodium carboxymethylcellulose (CMC) solid powder to be added in 100 ml beakers, it is ultrapure then to weigh 99 g
Water is added in beaker, is put into the magneton that length is 2 cm, is sealed beaker mouth with plastic film and rubber ring, beaker is placed in
On magnetic stirring apparatus, setting speed is 100 r/min, is stirred 12 hours at room temperature, and it is water-soluble that the CMC that mass fraction is 1% is made
Liquid.It accurately weighs quality accounting to be added in 50 ml vacuum stirring tank for the CMC aqueous solution of 2 wt%(12 g), then be added
Quality accounting is 3 wt%(0.36 g) mass fraction be 50 wt% SBR aqueous solution, set de-airing mixer revolving speed as 500
R/min stirs 30 min at room temperature, and the mixed solution of finely dispersed CMC and SBR is made.
B, cladding of the carbon nanotube (CNT) in active carbon (AC) particle surface
Accurately weighing quality accounting is 3.125 wt%(3.75 g) carbon nanotube (CNT) content be 5 wt% water system CNT slurry
Material, is added in mixed solution made from step A, sets de-airing mixer revolving speed as 500 r/min, be stirred at room temperature 30
Min, is made finely dispersed carbon nanotube (CNT) and the mixing of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) is molten
Liquid；Quality accounting is accurately weighed as active carbon (AC) solid powder of 90 wt%(5.4 g), it is molten to be added to above-mentioned mixing in three times
In liquid, de-airing mixer revolving speed being set as 500 r/min, is stirred at room temperature, stir 30 min every time, CNT is made and uniformly wraps
It is overlying on the mixed slurry of AC particle surface.
C, the preparation of carbon nano-fiber (CNF) dispersion liquid
It accurately weighs quality accounting and is added to 100 ml burning for carbon nano-fiber (CNF) powder of 0.625 wt%(0.0375 g)
In cup, the mixed acid of the concentrated sulfuric acid and concentrated nitric acid that 20 ml volume ratios are 3:1 is then added, is put into the magneton that length is 2 cm, uses
Plastic film and rubber ring seal beaker mouth, and beaker is placed in magnetic-mixing constant temperature water bath boiler, and setting speed is 60 r/
Min stirs 3 h at 60 DEG C, is then added to the CNF after cleaning to neutral (PH=7) with ultrapure water eccentric cleaning and is equipped with
In the beaker of 5 g ultrapure waters, add 8 mM/L(0.01 g) Surfactant SDS (SDS), ultrasound point
Uniform CNF dispersion liquid is made after dissipating 40 min.
D, the system of AC/CNT/CNF/SP/SBR/CMC=90/3.125/0.625/1.25/3/2 three-dimensional manometer combination electrode
It is standby
CNF dispersion liquid made from step C is added in mixed slurry made from step B, sets de-airing mixer revolving speed as 500
R/min is added quality accounting after 30 min are stirred at room temperature as the conductive agent SP of 1.25 wt%(0.075 g), sets vacuum
Blender revolving speed is 500 r/min, continues that three-dimensional manometer combination electrode slurry is made after stirring 60 min at room temperature, this is answered
It after composite electrode slurry vacuumizes 10 min of standing, is filtered with 100 mesh filter screen, gained slurry is coated on corrosive aluminum foil collection
On fluid, the roll-in after dry 3 h at 60 DEG C is punched into the round pole piece that diameter is 12 mm with slicer, then by pole piece
12 h are dried in vacuo at 60 DEG C, it is AC/CNT/CNF/SP/SBR/CMC(90/3.125/0.625/ that electrode component, which is made,
1.25/3/2) supercapacitor is with novel three-dimensional nanometer combined electrode (as shown in Fig. 1-a).
The preparation of (90/2.75/1/1.25/3/2) three-dimensional manometer combination electrode
A, the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
The mixed solution of finely dispersed CMC and SBR are prepared according to the method for 1.1 step A in embodiment 1.
B, the cladding of carbon nanotube (CNT) and redox graphene (rGO) in active carbon (AC) particle surface
A) graphite oxide the preparation of graphite oxide: is prepared with improved Hummers method: by 3 g scales under condition of ice bath
Graphite is added in the 69 ml concentrated sulfuric acids, then plus 9 g potassium permanganate (purity: 99.5 wt%) (Gao Meng is aoxidized to crystalline flake graphite
Sour potassium is slowly added to, and the temperature of guarantee system is lower than 20 DEG C), ice bath is removed, 35 ± 3 DEG C is heated in a water bath and keeps
30 min, being slowly added to 138 mL of ultrapure water makes the temperature of system reach 98 DEG C and keeps 15 min, continuously adds 420 mL
40 DEG C of warm water adds the remaining oxidant of hydrogen-peroxide reduction of 3 mL, 30 wt %, by acquired solution in room temperature condition
It after lower 24 h of strong stirring, is washed repeatedly with the HCl solution of 5 wt% and ultrapure water, until without SO in supernatant4 2-(use BaCl2
Examine) until, the graphite oxide solution of glassy yellow is obtained, gained graphite oxide solution is centrifuged, in 80 DEG C of 12 h of vacuum drying
Oxidation graphite solid is made afterwards.
B) cladding of carbon nanotube (CNT) and redox graphene (rGO) in active carbon (AC) particle surface: accurate to claim
Take by 1.2 step B a in embodiment 1) preparation quality accounting be 1 wt% graphite oxide (0.1 g), be added 250 ml burning
In cup, 100 g ultrapure waters are poured into, beaker mouth is covered with film, is put into ultrasonic machine, the water level of ultrasonic machine is allowed not have the water in beaker
, the hydrazine hydrate of 5 ml, 80 wt% is added after 30 min of ultrasound, it is 0.25 wt%(0.5 that quality accounting is added after reaction two minutes
G) CNT content is the water system CNT slurry of 5 wt%, after 30 min of ultrasound, addition quality accounting for 90 wt%(9 g) AC, into
Row stirs, then 4 h of ultrasound.With filtered on buchner funnel, and fall extra hydrazine hydrate with ultrapure water, is put into air dry oven
After 60 DEG C of 3 h of drying, it is transferred to vacuum drying oven, dry 12 h, grind after drying under the conditions of 60 DEG C, -0.8 MPa
To the composite material of AC/rGO/CNT.
C, AC/CNT/rGO/SP/SBR/CMC(90/2.75/1/1.25/3/2) electrode slurry preparation
Precise quality accounting is 2.5 wt%(3 g) CNT content be 5 wt% water system CNT slurry be added to step A system
In the CMC and SBR mixed solution obtained, de-airing mixer revolving speed is set as 500 r/min, after 30 min are stirred at room temperature, is divided
Three times be added quality accounting be 90 wt%(5.475 g) step B b) and made from AC/rGO/CNT composite material, setting vacuum stir
Mixing machine revolving speed is 500 r/min, is stirred at room temperature, and stirs 40 min every time, and it is 1.25 wt% that quality accounting is added later
The conductive agent SP of (0.075 g) sets de-airing mixer revolving speed as 500 r/min, and AC/CNT/rGO/ is made after stirring 60 min
SP/SBR/CMC(90/2.75/1/1.25/3/2) three-dimensional manometer combination electrode slurry.
D, AC/CNT/rGO/SP/SBR/CMC(90/2.75/1/1.25/3/2) three-dimensional manometer combination electrode preparation
It accurately weighs 4 g ultrapure waters to be added in combination electrode slurry made from step C, sets de-airing mixer revolving speed as 500
30 min are stirred at room temperature in r/min, and adjusting slurry solid content is 24%, vacuumize after standing 10 min, are carried out with 100 meshes
Gained slurry is coated on corrosive aluminum foil collector by filtering, and roll-in after dry 3 h, is punched into directly with slicer at 60 DEG C
Diameter is the round pole piece of 12 mm, is then dried in vacuo pole piece 12 hours at 60 DEG C, and it is AC/CNT/ that electrode component, which is made,
RGO/SP/SBR/CMC(90/2.75/1/1.25/3/2 supercapacitor) is with three-dimensional manometer combination electrode (such as Fig. 1-b institute
Show).
The preparation of (78.75/1.25/1.25/8.75/7/3) three-dimensional manometer combination electrode
A, the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
The CMC aqueous solution that mass fraction is 1% is made according to the method for 1.1 step A in embodiment 1, weighing quality accounting later is
3 wt%(18 g) the CMC solution and quality accounting be 7 wt%(0.84 g) mass fraction be 50 wt% SBR aqueous solution, according to
The method of 1.1 step A prepares the mixed solution of finely dispersed CMC and SBR in embodiment 1.
B, in-stiu coating of the redox graphene (rGO) in active carbon (AC) particle surface
Accurately weigh by 1.2 step B a in embodiment 1) method preparation quality accounting be 1.25 wt%(0.4 g) oxidation
Graphite is added to 30 min of ultrasound removing in the beaker equipped with 100 ml ultrapure waters, and being slowly added to quality accounting later is 78.75
Wt%(25.2 g) active carbon powder, carry out in-stiu coating of the graphene oxide in activated carbon granule surface, 90 min of ultrasound
Afterwards, the hydrazine hydrate ultrasound that 15 ml, 80 wt% is added restores 60 min, is then filtered, after 60 DEG C of 12 h of vacuum drying
The absorbent charcoal material (AC/rGO) of redox graphene cladding is obtained, accurately weighing quality accounting is 80 wt%(4.8 g)
AC/rGO solid powder is added in three times in mixed solution obtained by step A, sets de-airing mixer revolving speed as 500 r/
Min stirs 30 min every time at room temperature, and the mixed slurry of AC/rGO and CMC and SBR is made.
C, the preparation of carbon nano-fiber (CNF) dispersion liquid
Quality accounting is accurately weighed as the CNF of 1.25 wt%(0.09 g), is made equal according to the method for 1.1 step C in embodiment 1
Even CNF dispersion liquid.
D, AC/rGO/CNF/SP/SBR/CMC(78.75/1.25/1.25/8.75/7/3) three-dimensional manometer combination electrode system
It is standby
CNF dispersion liquid made from step C is added in mixed slurry made from step B, sets de-airing mixer revolving speed as 500
R/min is added quality accounting after 30 min are stirred at room temperature as the conductive agent SP of 8.75 wt%(0.525 g), sets vacuum
Blender revolving speed is 500 r/min, and supercapacitor three-dimensional manometer combination electrode slurry is made after 60 min are stirred at room temperature
Material, which is vacuumized after standing 10 min, is filtered with 100 mesh filter screen, and gained slurry is coated on corrosive aluminum foil
On collector, the roll-in after dry 3 h at 60 DEG C is punched into the round pole piece that diameter is 12 mm with slicer, then by pole
Piece is dried in vacuo 12 h at 60 DEG C, and it is AC/rGO/CNF/SP/SBR/CMC (78.75/1.25/1.25/ that electrode component, which is made,
8.75/7/3) supercapacitor is with three-dimensional manometer combination electrode (as shown in fig 1-c).
The preparation of (97.99/0.005/0.005/1/0.6/0.4) three-dimensional manometer combination electrode
A, the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
It accurately weighs 1 g sodium carboxymethylcellulose (CMC) solid powder to be added in 100 ml beakers, it is ultrapure then to weigh 99 g
Water is added in beaker, is put into the magneton that length is 2 cm, is sealed beaker mouth with plastic film and rubber ring, beaker is placed in
On magnetic stirring apparatus, setting speed is 100 r/min, is stirred 12 hours at room temperature, and it is water-soluble that the CMC that mass fraction is 1% is made
Liquid.Quality accounting is accurately weighed to be added to 50 ml vacuum for the CMC aqueous solution of 0.4 wt%(2.4 g) and 10 g ultrapure waters and stir
Mix in tank, then be added quality accounting be 0.6 wt%(0.072 g) mass fraction be 50 wt% SBR aqueous solution, set very
Empty blender revolving speed is 500 r/min, stirs 30 min at room temperature, the mixed solution of finely dispersed CMC and SBR is made.
B, cladding of the carbon nanotube (CNT) in active carbon (AC) particle surface
Accurately weighing quality accounting is 0.005 wt%(0.006 g) carbon nanotube (CNT) content be 5 wt% water system CNT slurry
Material, is added in mixed solution made from step A, sets de-airing mixer revolving speed as 500 r/min, be stirred at room temperature 30
Min, is made finely dispersed carbon nanotube (CNT) and the mixing of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) is molten
Liquid；Accurately weighing quality accounting is 97.99 wt%(5.8794 g) active carbon (AC) solid powder, it is added in three times above-mentioned mixed
It closes in solution, sets de-airing mixer revolving speed as 500 r/min, be stirred at room temperature, stir 30 min every time, it is equal that CNT is made
The even mixed slurry for being coated on AC particle surface.
C, the preparation of carbon nano-fiber (CNF) dispersion liquid
It accurately weighs quality accounting and is added to 100 ml burning for carbon nano-fiber (CNF) powder of 0.005 wt%(0.0003 g)
In cup, the mixed acid of the concentrated sulfuric acid and concentrated nitric acid that 20 ml volume ratios are 3:1 is then added, is put into the magneton that length is 2 cm, uses
Plastic film and rubber ring seal beaker mouth, and beaker is placed in magnetic-mixing constant temperature water bath boiler, and setting speed is 60 r/
Min stirs 3 h at 60 DEG C, is then added to the CNF after cleaning to neutral (PH=7) with ultrapure water eccentric cleaning and is equipped with
In the beaker of 5 g ultrapure waters, add 4 mM/L(0.005 g) Surfactant SDS (SDS), ultrasound point
Uniform CNF dispersion liquid is made after dissipating 30 min.
D, AC/CNT/CNF/SP/SBR/CMC=97.99/0.005/0.005/1/0.6/0.4 three-dimensional manometer combination electrode
Preparation
CNF dispersion liquid made from step C is added in mixed slurry made from step B, sets de-airing mixer revolving speed as 500
Quality accounting is added after 30 min are stirred at room temperature as the conductive agent SP of 1 wt%(0.06 g) in r/min, and setting is stirred under vacuum
Machine revolving speed is 500 r/min, continues that three-dimensional manometer combination electrode slurry is made after stirring 60 min at room temperature, by the compound electric
It after pole slurry vacuumizes 10 min of standing, is filtered with 100 mesh filter screen, gained slurry is coated on corrosive aluminum foil collector
On, the roll-in after dry 3 h at 60 DEG C is punched into the round pole piece that diameter is 12 mm with slicer, then by pole piece 60
12 h are dried in vacuo at DEG C, it is AC/CNT/CNF/SP/SBR/CMC(97.99/0.005/0.005/1/0.6/ that electrode component, which is made,
0.4) supercapacitor novel three-dimensional nanometer combined electrode.
(50/4/6/20/12/8) preparation of three-dimensional manometer combination electrode
A, the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
Quality accounting is accurately weighed as sodium carboxymethylcellulose (CMC) solid powder and 17 g ultrapure waters of 8 wt%(0.48 g)
It is added to 50 ml to be stirred under vacuum in tank, sets de-airing mixer revolving speed as 500 r/min, be added after stirring 60 min at room temperature
Quality accounting is 12 wt%(1.44 g) mass fraction be 50 wt% SBR aqueous solution, set de-airing mixer revolving speed as 500
R/min stirs 30 min at room temperature, and the mixed solution of finely dispersed CMC and SBR is made.
B, cladding of the carbon nanotube (CNT) in active carbon (AC) particle surface
Accurately weighing quality accounting is 4 wt%(4.8 g) carbon nanotube (CNT) content be 5 wt% water system CNT slurry, add
Enter into mixed solution made from step A, set de-airing mixer revolving speed as 500 r/min, 30 min are stirred at room temperature, makes
Obtain the mixed solution of finely dispersed carbon nanotube (CNT) and sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR)；Accurately
Weighing quality accounting is 50 wt%(3 g) active carbon (AC) solid powder, it is add to the above mixed solution in three times, setting is true
Empty blender revolving speed is 500 r/min, is stirred at room temperature, and stirs 30 min every time, and obtained CNT is uniformly wrapped on AC particle table
The mixed slurry in face.
C, the preparation of carbon nano-fiber (CNF) dispersion liquid
Carbon nano-fiber (CNF) powder that quality accounting is accurately weighed as 6 wt%(0.36 g) is added in 100 ml beakers, so
The mixed acid of the concentrated sulfuric acid and concentrated nitric acid that 20 ml volume ratios are 5:1 is added afterwards, is put into the magneton that length is 2 cm, it is thin with plastics
Film and rubber ring seal beaker mouth, and beaker is placed in magnetic-mixing constant temperature water bath boiler, and setting speed is 60 r/min, 60
3 h are stirred at DEG C, and then the CNF after cleaning is added to equipped with 5 g ultrapure waters to neutral (PH=7) with ultrapure water eccentric cleaning
Beaker in, add 20 mM/L(0.025 g) surfactant sodium dodecyl base benzene sulfonic acid sodium salt (SDBS), ultrasonic disperse 120
Uniform CNF dispersion liquid is made after min.
D, the preparation of the three-dimensional manometer combination electrode of AC/CNT/CNF/SP/SBR/CMC=50/4/6/20/12/8
CNF dispersion liquid made from step C is added in mixed slurry made from step B, sets de-airing mixer revolving speed as 500
Quality accounting is added after 30 min are stirred at room temperature as the conductive agent SP of 20 wt%(1.2 g) in r/min, and setting is stirred under vacuum
Machine revolving speed is 500 r/min, continues that three-dimensional manometer combination electrode slurry is made after stirring 60 min at room temperature, by the compound electric
It after pole slurry vacuumizes 10 min of standing, is filtered with 100 mesh filter screen, gained slurry is coated on corrosive aluminum foil collector
On, the roll-in after dry 3 h at 60 DEG C is punched into the round pole piece that diameter is 12 mm with slicer, then by pole piece 60
It is dried in vacuo 12 h at DEG C, electrode component is made as the super electricity of AC/CNT/CNF/SP/SBR/CMC(50/4/6/20/12/8)
Container novel three-dimensional nanometer combined electrode.
2, the test of supercapacitor novel three-dimensional nanometer combined electrode
The test of 2.1 high power scanning electron microscope (SEM)
The supercapacitor novel three-dimensional nanometer combined electrode that will be prepared by above-described embodiment 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) shape characteristic is carried out with high power scanning electron microscope (SEM)
Characterization test (such as attached drawing 1-a, 1-b, shown in 1-c).Test result shows: in combination electrode, CNT can equably be wrapped in AC
Particle surface, graphene sheet layer form close cladding on the surface AC, and CNF can play the role of connecting variable grain, nanometer
Carbon material (CNT+CNF or CNT+rGO or rGO+CNF) is constructed to form efficient three-dimensional conductive network together with conductive particle SP.
2.2 electrochemical property tests:
2.2.1 encapsulation
It, will be by the supercapacitor of embodiment 1 in the glove box of control oxygen (< 0.1 ppm) and moisture (< 0.1 ppm)
With high-performance novel three-dimensional manometer combination electrode, LIR2025 battery case, cellulose acetate membrane and 1 M [TEA] [BF4]/ACN
Electrolyte is assembled into button supercapacitor, is used for electrochemical property test after standing 1 h at room temperature.
2.2.2 electrochemical property test
A. ac impedance measurement: frequency range of the button supercapacitor that step 2.2.1 is encapsulated in the mHz of 100 kHz~10
It is interior, using the AC amplitude of 10 mV, carry out ac impedance measurement under open-circuit voltage (as shown in attached drawing 3,4).Test result table
It is bright, have benefited from nano-carbon material synergistic effect give full play to and combination electrode in efficient three-dimensional conductive network formation, it is compound
The charge transfer resistance and diffusion resistance of electrode significantly reduce, electric conductivity is obviously improved.
B. multiplying power is tested: the button supercapacitor that step 2.2.1 is encapsulated uses in the voltage range of 0~2.7 V
0.5~80 A g-1Current density carry out high rate performance test (as shown in attached drawing 5,6).Test result shows: having benefited from nanometer
Carbon material synergistic effect give full play to and combination electrode in efficient three-dimensional conductive network formation, the high rate performance of combination electrode
It greatly improves, in 80 A g-1Current density under, three kinds of novel three-dimensional nanometer combined electrode (AC/ being prepared by embodiment 1
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)) be respectively provided with 71.92%,
87.28%, 79.54% high capacity conservation rate, shows excellent multiplying power property.
C. cyclic voltammetry: the button supercapacitor that step 2.2.1 is encapsulated in the voltage range of 0~2.7 V,
Using 500 mV S-1Sweep speed carry out cyclic voltammetry (as shown in attached drawing 7,8).Test result shows: having benefited from nano-sized carbon
Material synergistic effect give full play to and combination electrode in efficient three-dimensional conductive network formation, the volt-ampere curve of combination electrode exists
500 mV S-1Sweep greatly and still keep good rectangle under speed, show excellent fast response characteristic.
D. cycle life test: the button supercapacitor that step 2.2.1 is encapsulated in the voltage range of 0~2.7 V,
Using 10 A g-1Current density carry out cycle life test (as shown in attached drawing 9,10).Test result shows: having benefited from nanometer
Carbon material synergistic effect give full play to and combination electrode in efficient three-dimensional conductive network formation, combination electrode shows splendid
Cyclical stability.In 10 A g-1Current density under, the novel three-dimensional nanometer combined electrode (AC/ that is prepared by embodiment 1
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) it) is respectively provided with 86.37% and 79.44% high capacity conservation rate after 30000 circulations, is prepared by embodiment 1 new
Type three-dimensional manometer combination electrode (AC/rGO/CNF/SP/SBR/CMC(78.75/1.25/1.25/8.75/7/3)) it follows for 15000 times
There is 91.25% high capacity conservation rate after ring.
Embodiment 2, the preparation and test of lithium ion battery of the present invention high-performance novel three-dimensional manometer combination electrode:
1, the preparation of lithium ion battery high-performance novel three-dimensional manometer combination electrode
1.1 redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) three-dimensional manometer combination electrode (LFP/rGO/CNT/
SP/KS6/PVDF=90/1/1/3/1/4) preparation
A, the preparation of graphite oxide
According to 1.2 step B a in embodiment 1) method carry out graphite oxide preparation.
B, LFP/rGO(90/1) composite material preparation:
In the beaker of 250 mL, the water and hydrazine solution of 80 wt% of ultrapure water and 10 mL of 100 mL is added, in above-mentioned solution
It is middle that quality accounting prepared by step A is added as the graphite oxide of 1 wt%(0.2 g), after 10 min of ultrasonic disperse, quality is added and accounts for
Than the LFP material for 90 wt%(18 g), after continuing 4 h of ultrasound, with milli-Q water, filtering, 12 are dried in vacuo at 80 DEG C
LFP/rGO(90/1 is made after h) composite material.
C, the preparation of the electrode slurry of LFP/rGO/CNT/SP/KS6/PVDF=90/1/1/3/1/4
In the vacuum stirring tank of 50 mL, 20 mL NMP are added, then weighs quality accounting and consolidates for the PVDF of 4 wt%(0.8 g)
Body is added in above-mentioned nmp solution, and after stirring 90 min, additions quality accounting is 1 wt%(4 g) the NMP slurry (quality of CNT
Score is 5 wt%), and quality accounting is separately added into after 60 min of stirring as the conductive agent SP and quality accounting of 3 wt%(0.6 g) and is
1 wt%(0.2 g) conductive agent KS6, continue stir 60 min, divide later 4 times be added step B preparation quality accountings be 91
Wt%(18.2 g) LFP/rGO composite material, every time stir 30 min, be made LFP/rGO/CNT/SP/KS6/PVDF=90/
1/1/3/1/4 electrode slurry.
D, the preparation of the combination electrode of LFP/rGO/CNT/SP/KS6/PVDF=90/1/1/3/1/4
Electrode slurry made from step C is vacuumized after standing 10 min with 120 mesh screens, gained slurry is coated uniformly on aluminium
On foil, the roll-in after 80 DEG C of dry 2 h is punched into the round pole piece that diameter is 14 mm with slicer, then by pole piece 120
It is dried in vacuo 12 h at DEG C and obtains redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) (LFP/rGO/CNT/
SP/KS6/PVDF=90/1/1/3/1/4) three-dimensional manometer combination electrode (as shown in Figure 11-a).
Graphene oxide/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) three-dimensional manometer combination electrode (LFP/GO/CNT/
SP/KS6/PVDF=90/1/1/3/1/4) preparation
A, the preparation of graphene oxide dispersion:
10 mL nmp solutions are added in the brown bottle of 60 mL, are added in the above solution according to 1.2 step B in embodiment 1
A) the quality accounting of method preparation is 1 wt%(0.2 g) graphite oxide, after 60 min of ultrasonic disperse, form graphite oxide
The dispersion liquid of alkene.
B, SP/KS6/PVDF=90/1/1/3/1/4 LFP/GO/CNT/) electrode slurry preparation
In the vacuum stirring tank of 50 mL, 10 mL NMP are added, then weighs quality accounting and consolidates for the PVDF of 4 wt%(0.8 g)
Body is added in above-mentioned nmp solution, and 90 min of stirring dissolve PVDF all, and the oxygen as made from step A is added into agitator tank
Graphite alkene dispersion liquid, after stirring 60 min, additions quality accounting is 1 wt%(4 g) the NMP slurry (mass fraction 5 of CNT
Wt%), continuing to stir 60 min, then being separately added into quality accounting is 3 wt%(0.6 g) conductive agent SP and quality accounting be 1 wt%
The conductive agent KS6 of (0.2 g) stirs 60 min, and then dividing 4 addition quality accountings is 90 wt%(18 g) LFP positive electrode,
The electrode slurry of LFP/GO/CNT/SP/KS6/PVDF=90/1/1/3/1/4 is made in 30 min of stirring every time.
C, the preparation of the combination electrode of LFP/GO/CNT/SP/KS6/PVDF=90/1/1/3/1/4
The preparation that above-mentioned electrode slurry is carried out to electrode according to the method for 1.1 step D in embodiment 2, is made graphene oxide/carbon
The three-dimensional manometer of nanotube coated LiFePO 4 for lithium ion batteries (organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/GO/CNT/) is multiple
Composite electrode (as shown in Figure 11-b).
Redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) three-dimensional manometer combination electrode (LFP/rGO/
SP/KS6/PVDF=90/1/1/3/1/4 CNT/) preparation
A, the preparation of redox graphene
Accurately weigh according to 1.2 step 2 B a in embodiment 1) method preparation 1 g of graphite oxide be placed in porcelain boat, be put into
In tube furnace, under the atmosphere of nitrogen (throughput: 100 mL/min), from 25 DEG C of the room temperature heating rate liters with 5 DEG C/min
To 800 DEG C, and 1 h is kept, after cooled to room temperature, redox graphene powder is made in collection material.
B, the preparation of redox graphene dispersion liquid
10 mL nmp solutions are added in the brown bottle of 60 mL, it is 1 wt%(0.2 g that quality accounting is added in the above solution)
The dispersion liquid of redox graphene is made after 60 min of ultrasonic disperse for the redox graphene powder as made from step A.
C, the preparation of the electrode slurry of LFP/rGO/CNT/ SP/KS6/PVDF=90/1/1/3/1/4
The preparation of electrode slurry is carried out according to the method for 1.2 step B in embodiment 2, and LFP/rGO/CNT/ SP/KS6/ is made
The electrode slurry of PVDF=90/1/1/3/1/4.
D, the preparation of the combination electrode of LFP/rGO/CNT/ SP/KS6/PVDF=90/1/1/3/1/4
The preparation that above-mentioned electrode slurry is carried out to electrode according to the method for 1.1 step D in embodiment 2, is made reduction-oxidation graphite
Alkene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/rGO/CNT/) three-dimensional
Nanometer combined electrode (as shown in Figure 11-c).
Redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) three-dimensional manometer combination electrode (LFP/rGO/
CNT/SP/KS6/PVDF=97.99/0.005/0.005/0.75/0.25/1) preparation
A, the preparation of graphite oxide
According to 1.2 step B a in embodiment 1) method carry out graphite oxide preparation.
B, LFP/rGO(90/1) composite material preparation:
In the beaker of 250 mL, the ultrapure water of 100 mL is added, the water and hydrazine solution of 0.5 mL, 80 wt% is added, above-mentioned
The quality accounting that step A preparation is added in solution is 0.005 wt%(0.001 g) graphite oxide, after 10 min of ultrasonic disperse,
Addition quality accounting is the LFP material of 97.99 wt%(19.598 g), after continuing 3 h of ultrasound, with milli-Q water, is filtered,
LFP/rGO(97.99/0.005 is made after 80 DEG C of 12 h of vacuum drying) composite material.
C, the preparation of LFP/rGO/CNT/SP/KS6/PVDF=97.99/0.005/0.005/0.75/0.25/1 electrode slurry
In the vacuum stirring tank of 50 mL, 20 mL NMP are added, then weighs quality accounting and consolidates for the PVDF of 1 wt%(0.2 g)
Body is added in above-mentioned nmp solution, and after stirring 90 min, additions quality accounting is 0.005 wt%(0.1 g) the NMP slurry of CNT
(mass fraction be 5 wt%), stirring and being separately added into quality accounting after 60 min is 0.75 wt%(0.15 g) conductive agent SP and
Quality accounting is the conductive agent KS6 of 0.25 wt%(0.05 g), continues to stir 60 min, divides 4 times later and step B preparation is added
Quality accounting is the LFP/rGO composite material of 97.995 wt%(19.599 g), stirs 30 min every time, and LFP/rGO/ is made
CNT/SP/KS6/PVDF=97.99/0.005/0.005/0.75/0.25/1 electrode slurry.
D, the preparation of LFP/rGO/CNT/SP/KS6/PVDF=97.99/0.005/0.005/0.75/0.25/1 combination electrode
Electrode slurry made from step C is vacuumized after standing 10 min with 120 mesh screens, gained slurry is coated uniformly on aluminium
On foil, the roll-in after 80 DEG C of dry 2 h is punched into the round pole piece that diameter is 14 mm with slicer, then by pole piece 120
It is dried in vacuo 12 h at DEG C and obtains redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) (LFP/rGO/CNT/
SP/KS6/PVDF=97.99/0.005/0.005/0.75/0.25/1) three-dimensional manometer combination electrode.
Redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) three-dimensional manometer combination electrode (LFP/rGO/
CNT/SP/KS6/PVDF=50/6/4/15/5/20) preparation
A, the preparation of redox graphene
Accurately weigh according to 1.2 step 2 B a in embodiment 1) method preparation quality accounting be 6 wt%(1.2 g) oxygen
Graphite is placed in porcelain boat, is put into tube furnace, under the atmosphere of nitrogen (throughput: 100 mL/min), from 25 DEG C of room temperature with
The heating rate of 5 DEG C/min is raised to 800 DEG C, and keeps 1 h, and after cooled to room temperature, reduction-oxidation is made in collection material
Graphene powder.
B, the preparation of redox graphene dispersion liquid
10 mL nmp solutions are added in the brown bottle of 60 mL, the reduction-oxidation as made from step A is added in the above solution
The dispersion liquid of redox graphene is made after 120 min of ultrasonic disperse for graphene powder.
C, the preparation of the electrode slurry of LFP/rGO/CNT/ SP/KS6/PVDF=50/6/4/15/5/20
In the vacuum stirring tank of 50 mL, 10 mL NMP are added, then weigh quality accounting as the PVDF solid of 20 wt%(4 g)
It is added in above-mentioned nmp solution, 90 min of stirring dissolve PVDF all, are added into agitator tank and aoxidize as made from step A
Graphene dispersing solution, after stirring 60 min, additions quality accounting is 4 wt%(16 g) the NMP slurry (mass fraction 5 of CNT
Wt%), continuing to stir 60 min, then being separately added into quality accounting is 15 wt%(3 g) conductive agent SP and quality accounting be 5 wt%
The conductive agent KS6 of (1 g) stirs 60 min, and then dividing 4 addition quality accountings is 50 wt%(10 g) LFP positive electrode, often
The electrode slurry of LFP/GO/CNT/SP/KS6/PVDF=50/6/4/15/5/20 is made in 30 min of secondary stirring.
D, the preparation of the combination electrode of LFP/GO/CNT/SP/KS6/PVDF=50/6/4/15/5/20
The preparation that above-mentioned electrode slurry is carried out to electrode according to the method for 1.1 step D in embodiment 2, is made graphene oxide/carbon
The three-dimensional manometer of nanotube coated LiFePO 4 for lithium ion batteries (organic phase) (SP/KS6/PVDF=50/6/4/15/5/20 LFP/GO/CNT/)
Combination electrode.
2, the test of lithium ion battery novel three-dimensional nanometer combined electrode
The test of 2.1 high power scanning electron microscope (SEM)
By the lithium ion battery prepared by above-described embodiment 2, with novel three-dimensional nanometer combined electrode, (redox graphene/carbon is received
Mitron coated LiFePO 4 for lithium ion batteries (water phase) combination electrode (LFP/rGO/CNT/SP/KS6/PVDF=90/1/1/3/1/4), graphite oxide
Alkene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/GO/CNT/), oxygen reduction
Graphite alkene/carbon nanotube coated LiFePO 4 for lithium ion batteries (organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/rGO/CNT/))
The characterization test (such as attached drawing 11-a, 11-b, shown in 11-c) of shape characteristic is carried out with high power scanning electron microscope (SEM).Test result
Show: in combination electrode, graphene sheet layer can form close cladding on the surface LFP, and CNT can be evenly dispersed in LFP
Between particle, and play the role of the different LFP particles of connection, nano-carbon material (CNT+rGO or CNT+GO) and conductive particle SP
And KS6 constructs to form efficient three-dimensional conductive network together.
Electrochemical property test
2.2.1 encapsulation
In the glove box of control oxygen (< 0.1 ppm) and moisture (< 0.1 ppm), the lithium ion that will be prepared by embodiment 2
Battery high-performance novel three-dimensional manometer combination electrode (as anode), lithium piece (as cathode), LIR2025 battery case, PP/
PE/PP diaphragm and 1 M LiPF6/ EC-EMC-DMC(volume ratio 1:1:1) electrolyte is assembled into fastening lithium ionic cell, in room temperature
Electrochemical property test is used for after 12 h of lower standing.
2.2.2 electrochemical property test
A. ac impedance measurement: frequency range of the fastening lithium ionic cell that step 2.2.1 is encapsulated in the mHz of 100 kHz~1
It is interior, using the AC amplitude of 10 mV, ac impedance measurement (as shown in Fig. 12) is carried out under open-circuit voltage.Test result table
It is bright, have benefited from nano-carbon material synergistic effect give full play to and combination electrode in efficient three-dimensional conductive network formation, it is compound
The charge transfer resistance of electrode significantly reduces, electric conductivity is obviously improved.
B. multiplying power is tested: the fastening lithium ionic cell that 2.2.1 step is encapsulated is in the voltage range of 2~4 V, in room temperature
Under the conditions of, with 0.2 C charging, 0.2 C, 1 C, 2 C are carried out respectively, and the electric discharge of 3 C, 5 C, 7 C, the different multiplyings such as 10 C are surveyed
Examination, and recycled 5 times (as shown in Fig. 13) under each multiplying power.Test result shows: having benefited from nano-carbon material synergistic effect
Give full play to and combination electrode in efficient three-dimensional conductive network formation, the high rate performance of combination electrode greatly improves, by implementing
(redox graphene/carbon nanotube coated LiFePO 4 for lithium ion batteries (water phase) is multiple for three kinds of novel three-dimensional nanometer combined electrodes prepared by example 2
Composite electrode (LFP/rGO/CNT/SP/KS6/PVDF=90/1/1/3/1/4), graphene oxide/carbon nanotube coated LiFePO 4 for lithium ion batteries
(organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/GO/CNT/), redox graphene/carbon nanotube coat phosphorus
Sour iron lithium (organic phase) (SP/KS6/PVDF=90/1/1/3/1/4 LFP/rGO/CNT/)) under 1 C current density, have respectively
There are 138.94 mAh g-1、135.73 mAh g-1、137.49 mAh g-1Specific discharge capacity, and it is close in the high current of 7 C
Under degree, the capacity retention ratio of three kinds of combination electrodes is respectively 47%, 41%, 46%(it is as shown in Fig. 13), show more excellent
Multiplying power property.
Embodiment 3
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nanotube (CNT) 0.005%,
Carbon nano-fiber (CNF) or graphene (Graphene) 0.005%, carbon black 1%, butadiene-styrene rubber (SBR) binder 1%, active powdered carbon
97.99%.Supercapacitor of the present invention is prepared by technique used in embodiment 1.
Embodiment 4
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nano-fiber (CNF) 5%, carbon
Nanotube (CNT) or graphene (Graphene) 5%, acetylene black 20%, butadiene rubber (BDR) binder 20%, activated carbon fibre
50%.Supercapacitor of the present invention is prepared by technique used in embodiment 1.
Embodiment 5
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nanotube (CNT) 2%, graphite
Alkene (Graphene) 3%, carbon black 7%, electrically conductive graphite 3%, polyvinyl alcohol (PVA) 5%, polyvinylidene fluoride (PVDF) binder 5%,
Active powdered carbon 75%.Supercapacitor of the present invention is prepared by technique used in embodiment 1.
Embodiment 6
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nano-fiber (CNF) 1%, carbon
Nanotube (CNT) 2%, carbon black 3%, conductive Carbon fibe 5%, acetylene black 4%, polyvinylidene fluoride (PVDF) 5%, polytetrafluoroethylene (PTFE)
(PTFE) 5%, polyvinyl alcohol (PVA) 5%, carbon aerogels 15%, porous graphite 25%, mesoporous carbon 30%.By technique used in embodiment 1
Prepare supercapacitor of the present invention.
Embodiment 7
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.5%, carbon nano-fiber (CNF) 0.5%, carbon nanotube (CNT) 1.5%, carbon black 1.5%, electrically conductive graphite 2.5%, conductive Carbon fibe
3.5%, acetylene black 3%, polyvinylidene fluoride (PVDF) 5%, sodium carboxymethylcellulose (CMC) 3%, polyvinyl alcohol (PVA) 4%, propylene
Sour resin (AAP) 6%, active carbon cloth 12%, activated carbon fibre 35%, porous hard carbon 22%.This hair is prepared by technique used in embodiment 1
Bright supercapacitor.
Embodiment 8
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.8%, carbon nano-fiber (CNF) 0.2%, carbon nanotube (CNT) 1.0%, carbon black 1.0%, electrically conductive graphite 1.0%, conductive Carbon fibe
1.5%, acetylene black 1.5%, polyvinylidene fluoride (PVDF) 1%, polytetrafluoroethylene (PTFE) 3%, sodium carboxymethylcellulose (CMC)
2%, polyvinyl alcohol (PVA) 1%, acroleic acid resin (AAP) 2%, active powdered carbon 15%, active carbon cloth 18%, activated carbon fibre 28%, more
Hole graphite 12%, carbon aerogels 11%.Supercapacitor of the present invention is prepared by technique used in embodiment 1.
Embodiment 9
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nanotube (CNT) 0.005%,
Carbon nano-fiber (CNF) or graphene (Graphene) 0.005%, carbon black 1%, butadiene-styrene rubber (SBR) binder 1%, graphite
92.99%；5% redox graphene dispersion liquid.Lithium ion battery of the present invention is prepared by technique used in embodiment 2.
Embodiment 10
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nano-fiber (CNF) 4.5%,
Carbon nanotube (CNT) or graphene (Graphene) 4.5%, acetylene black 18%, butadiene rubber (BDR) binder 18%, ferric phosphate
Lithium 13%, cobalt acid lithium 12%, ternary NCM 20%；10% redox graphene dispersion liquid.This hair is prepared by technique used in embodiment 2
Bright lithium ion battery.
Embodiment 11
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nanotube (CNT) 2%, graphite
Alkene (Graphene) 2.5%, carbon black 6%, electrically conductive graphite 2.5%, polyvinyl alcohol (PVA) 4%, polyvinylidene fluoride (PVDF) binder
5%, LiMn2O4 16%, nickel ion doped 15%, cobalt acid lithium 20%, ternary NCA 22%；5% graphene oxide dispersion.By 2 institute of embodiment
Lithium ion battery of the present invention is prepared with technique.
Embodiment 12
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nano-fiber (CNF) 1%, carbon
Nanotube (CNT) 2%, carbon black 3%, conductive Carbon fibe 4%, acetylene black 3%, polyvinylidene fluoride (PVDF) 4%, polytetrafluoroethylene (PTFE)
(PTFE) 4%, polyvinyl alcohol (PVA) 4%, graphite 15%, silicon 17%, silicon/carbon composite 15%, lithium titanate 18%；10% graphite oxide
Alkene dispersion liquid.Lithium ion battery of the present invention is prepared by technique used in embodiment 2.
Embodiment 13
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.5%, carbon nano-fiber (CNF) 0.5%, carbon nanotube (CNT) 1.5%, carbon black 1.5%, electrically conductive graphite 2.5%, conductive Carbon fibe
3.5%, acetylene black 3%, polyvinylidene fluoride (PVDF) 5%, sodium carboxymethylcellulose (CMC) 3%, polyvinyl alcohol (PVA) 4%, propylene
Sour resin (AAP) 6%, cobalt acid lithium 12%, LiMn2O4 35%, ternary NCA 22%.By technique used in embodiment 2 prepare lithium of the present invention from
Sub- battery.
Embodiment 14
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.8%, carbon nano-fiber (CNF) 0.2%, carbon nanotube (CNT) 1.0%, carbon black 1.0%, electrically conductive graphite 1.0%, conductive Carbon fibe
1.5%, acetylene black 1.5%, polyvinylidene fluoride (PVDF) 1%, polytetrafluoroethylene (PTFE) 3%, sodium carboxymethylcellulose (CMC)
2%, polyvinyl alcohol (PVA) 1%, acroleic acid resin (AAP) 2%, LiFePO4 33.99%, cobalt acid lithium 17%, LiMn2O4 15%, nickel manganese
Sour lithium 18%；0.01% redox graphene dispersion liquid.Lithium ion battery of the present invention is prepared by technique used in embodiment 2.
Embodiment 15
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.8%, carbon nano-fiber (CNF) 0.2%, carbon nanotube (CNT) 1.0%, carbon black 1.0%, electrically conductive graphite 1.0%, conductive Carbon fibe
1.5%, acetylene black 1.5%, polyvinylidene fluoride (PVDF) 1%, polytetrafluoroethylene (PTFE) 3%, sodium carboxymethylcellulose (CMC)
2%, polyvinyl alcohol (PVA) 1%, acroleic acid resin (AAP) 1.99%, soft carbon 20%, graphite 20%, mesocarbon microspheres 15%, silicon/carbon
Composite material 15%, silicon 14%；0.01% graphene oxide dispersion prepares lithium-ion electric of the present invention by technique used in embodiment 2
Pond.
Embodiment 16
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: graphene (Graphene)
0.5%, carbon nano-fiber (CNF) 0.5%, carbon nanotube (CNT) 1.5%, carbon black 1.5%, electrically conductive graphite 2.5%, conductive Carbon fibe
3.5%, acetylene black 3%, polyvinylidene fluoride (PVDF) 5%, sodium carboxymethylcellulose (CMC) 3%, polyvinyl alcohol (PVA) 4%, propylene
Sour resin (AAP) 6%, graphene in-stiu coating lithium ion battery electrode material 69%.The present invention is prepared by technique used in embodiment 2
Lithium ion battery.
Embodiment 17
Each component ratio by mass percentage in the three-dimensional manometer combination electrode material are as follows: carbon nano-fiber (CNF) 1%, carbon
Nanotube (CNT) 2%, carbon black 3%, conductive Carbon fibe 5%, acetylene black 4%, polyvinylidene fluoride (PVDF) 5%, polytetrafluoroethylene (PTFE)
(PTFE) 5%, polyvinyl alcohol (PVA) 5%, graphene in-stiu coating lithium ion battery electrode material 70%.By 2 recruitments of embodiment
Skill prepares lithium ion battery of the present invention.
Comparative experiments example 1
The preparation and test of the regular activated carbon resistance rod of supercapacitor
1, the preparation of the regular activated carbon resistance rod of supercapacitor
The preparation of 1.1 regular power type activated carbon electrodes (AC/SP/SBR/CMC=90/5/3/2)
1.1.1 the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
The mixed solution of finely dispersed CMC and SBR are made according to the method for 1.1 step A in embodiment 1, and it is super that 7 g are added
Pure water adjusts solution solid content.
1.1.2 the preparation of regular power type activated carbon electrodes (AC/SP/SBR/CMC=90/5/3/2) slurry
Quality accounting is accurately weighed as the conductive agent SP of 5 wt%(0.3 g), is added to CMC's made from step 1.1.1 and SBR
In mixed solution, de-airing mixer revolving speed is set as 500 r/min, 60 min are stirred at room temperature, accurately weigh quality later
Accounting is the AC solid powder of 90 wt%(5.4 g), is add to the above mixed solution in three times, and de-airing mixer revolving speed is set
It for 500 r/min, is stirred at room temperature, stirs 30 min every time, regular power type activated carbon electrodes slurry is made.
1.1.3 the preparation of regular power type activated carbon electrodes (AC/SP/SBR/CMC=90/5/3/2)
Regular power type activated carbon electrodes slurry made from 1.1.2 is vacuumized after standing 10 min, was carried out with 100 meshes
Filter, gained slurry are coated on corrosive aluminum foil collector, and roll-in after dry 3 h, is rushed combination electrode with slicer at 60 DEG C
It is cut into the round pole piece that diameter is 12 mm, pole piece is then dried in vacuo 12 h at 60 DEG C, supercapacitor is made with often
It advises energy type activated carbon electrodes (AC/SP/SBR/CMC=90/5/3/2) (as shown in Fig. 2-a).
The preparation of 1.2 ordinary power type activated carbon electrodes (AC/SP/SBR/CMC=80/10/7/3)
1.2.1 the preparation of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixed solution
The mixed solution of finely dispersed CMC and SBR are prepared according to the method for 1.3 step A in embodiment 1.
1.2.2 the preparation of ordinary power type active carbon (AC/SP/SBR/CMC=80/10/7/3) electrode slurry
Quality accounting is accurately weighed as the conductive agent SP of 10 wt%(0.6 g), is added to CMC's made from step 1.2.1 and SBR
In mixed solution, de-airing mixer revolving speed is set as 500 r/min, 60 min are stirred at room temperature；Quality is accurately weighed later
Accounting is the AC solid powder of 80 wt%(4.8 g), is add to the above mixed solution in three times, and de-airing mixer revolving speed is set
It for 500 r/min, is stirred at room temperature, stirs 30 min every time, ordinary power type activated carbon electrodes slurry is made.
1.2.3 the preparation of ordinary power type activated carbon electrodes (AC/SP/SBR/CMC=80/10/7/3)
Ordinary power type activated carbon electrodes slurry made from 1.2.2 is vacuumized after standing 10 min, was carried out with 100 meshes
Filter, gained slurry are coated on corrosive aluminum foil collector, and the roll-in after dry 3 h at 60 DEG C, being punched into diameter with slicer is
The round pole piece of 12 mm, is then dried in vacuo 12 h for pole piece at 60 DEG C, and it is living with ordinary power type that supercapacitor is made
Property carbon resistance rod (AC/SP/SBR/CMC=80/10/7/3) (as shown in Fig. 2-b).
, supercapacitor conventional activated carbon electrode test
The test of 2.1 high power scanning electron microscope (SEM)
By the supercapacitor prepared by above-mentioned comparative experiments example 1 with regular power type activated carbon electrodes (AC/SP/SBR/CMC=
90/5/3/2), ordinary power type activated carbon electrodes (AC/SP/SBR/CMC=80/10/7/3) use high power scanning electron microscope (SEM)
Carry out the characterization test of shape characteristic.Test result shows: in regular activated carbon resistance rod, conductive network is completely by conductive agent SP
The reunion of grain and formed, and SP particle agglomeration with AC is intergranular contacts poor (as shown in attached drawing 2-a, 2-b), be unable to shape
At leading efficient conductive network.
2.2 electrochemical property tests:
2.2.1 encapsulation
It, will be by the super electricity of comparative experiments example 1 in the glove box of control oxygen (< 0.1 ppm) and moisture (< 0.1 ppm)
The regular activated carbon resistance rod of container, LIR2025 battery case, cellulose acetate membrane and 1 M [TEA] [BF4]/ACN electrolyte group
Button supercapacitor is dressed up, is used for electrochemical property test after standing 1 h at room temperature.
2.2.2 electrochemical property test
A. ac impedance measurement: frequency range of the button supercapacitor that step 2.2.1 is encapsulated in the mHz of 100 kHz~10
It is interior, using the AC amplitude of 10 mV, carry out ac impedance measurement under open-circuit voltage (as shown in attached drawing 3,4).Test result table
It is bright, since the conductive network of regular activated carbon resistance rod is only formed by SP particle agglomeration, so that the charge transfer resistance of the electrode
With diffusion resistance is relatively large, electric conductivity is poor.
B. multiplying power is tested: the button supercapacitor that step 2.2.1 is encapsulated uses in the voltage range of 0~2.7 V
0.5~80 A g-1Current density carry out high rate performance test (as shown in attached drawing 5,6).Test result shows: due to conventional work
Property carbon resistance rod conductive network be only made of SP particle agglomeration, and SP particle agglomeration and AC it is intergranular contact it is poor,
Poorly conductive, so that the high rate performance of two kinds of regular activated carbon resistance rods is relatively poor.In 80 A g-1Current density under, it is conventional
The capacity retention ratio of energy type activated carbon electrodes only has 55.29%(attached drawing 5), the capacity of ordinary power type activated carbon electrodes is kept
Rate only has 54.51%(attached drawing 6).
C. cyclic voltammetry: the button supercapacitor that step 2.2.1 is encapsulated in the voltage range of 0~2.7 V,
Using 500 mV S-1Sweep speed carry out cyclic voltammetry (as shown in attached drawing 7,8).Test result shows: due to regular activated
The conductive network of carbon resistance rod is only made of SP particle agglomeration, poorly conductive, so that the volt-ampere curve of the electrode is in 500 mV S-1
Greatly sweep substantial deviation rectangle under speed, fast response characteristic is poor.
D. cycle life test: the button supercapacitor that step 2.2.1 is encapsulated in the voltage range of 0~2.7 V,
Using 10 A g-1Current density carry out cycle life test (as shown in attached drawing 9,10).Test result shows: due to conventional work
Property carbon resistance rod conductive network only be made of SP particle agglomeration, poorly conductive, high rate performance are poor so that the electrode show compared with
The cyclical stability of difference.In 10 A g-1Current density under, regular power type activated carbon electrodes 30000 times circulation after capacity
Conservation rate is only 69.54%(attached drawing 9), ordinary power type activated carbon electrodes 15000 times circulation after capacity retention ratio be only
82.47%(attached drawing 10).
Comparative experiments example 2
The preparation and test of lithium ion battery conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/3/1/4)
1, the preparation of lithium ion battery conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/3/1/4)
1.1.1 the preparation of lithium ion battery conventional phosphoric acid iron lithium electrode slurry
In the agitator tank of 50 mL, the NMP of 30 mL is added, then weighs quality accounting and adds for the PVDF solid of 4 wt%(0.8 g)
Enter into above-mentioned nmp solution, stir 90 min, dissolve PVDF all, additions quality accounting is 3 wt%(0.6 g) conduction
Agent SP and quality accounting are the conductive agent KS6 and 90 min of stirring of 1 wt%(0.2 g), so that conductive agent is uniformly dispersed, weigh quality
Accounting is added in above-mentioned solution in four times for the LFP material of 92 wt%(18.4 g), stirs 30 min every time, and lithium ion is made
Battery conventional phosphoric acid iron lithium electrode slurry.
1.1.2 the preparation of lithium ion battery conventional phosphoric acid iron lithium electrode
The preparation that above-mentioned electrode slurry is carried out to electrode according to the method for 1.1 step D in embodiment 2 is made lithium ion battery and uses
Conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/3/1/4) (as shown in Figure 11-d).
2, the test of lithium ion battery conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/3/1/4)
The test of 2.1 high power scanning electron microscope (SEM)
By the lithium ion battery prepared by above-mentioned comparative experiments example 2 conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/
3/1/4) characterization test of shape characteristic is carried out with high power scanning electron microscope (SEM) (as shown in attached drawing 11-d).Test result shows:
In conventional phosphoric acid iron lithium electrode, conductive network is formed by conductive agent SP and KS6 particle completely, and between SP and KS6 and LFP particle
Contact it is poor, efficient conductive network cannot be formed.
2.2 electrochemical property test
2.2.1 encapsulation
In the glove box of control oxygen (< 0.1 ppm) and moisture (< 0.1 ppm), the lithium that will be prepared by comparative experiments example 2
Ion battery conventional phosphoric acid iron lithium electrode (LFP/SP/KS6/PVDF=92/3/1/4) (as anode), lithium piece are (as negative
Pole), LIR2025 battery case, PP/PE/PP diaphragm and 1 M LiPF6/ EC-EMC-DMC(volume ratio 1:1:1) electrolyte is assembled into
Fastening lithium ionic cell is used for electrochemical property test after standing 12 h at room temperature.
2.2.2 electrochemical property test
A. ac impedance measurement: frequency range of the fastening lithium ionic cell that step 2.2.1 is encapsulated in the mHz of 100 kHz~1
It is interior, using the AC amplitude of 10 mV, ac impedance measurement (as shown in Fig. 12) is carried out under open-circuit voltage.Test result table
It is bright, since in conventional phosphoric acid iron lithium electrode, conductive network is formed by conductive agent SP and KS6 particle completely, and SP and KS6 with
The intergranular contact of LFP is poor, efficient conductive network cannot be formed, so that the charge transfer resistance of the electrode is larger, conductive
Property is poor.
B. multiplying power is tested: the fastening lithium ionic cell that step 2.2.1 is encapsulated is in the voltage range of 2~4 V, in room temperature
Under the conditions of, with 0.2 C charging, 0.2 C, 1 C, 2 C are carried out respectively, and the electric discharge of 3 C, 5 C, 7 C, the different multiplyings such as 10 C are surveyed
Examination, and recycled 5 times (as shown in Fig. 13) under each multiplying power.Test result shows: conductive due in conventional phosphoric acid iron lithium electrode
Network is formed by conductive agent SP and KS6 particle completely, and SP and KS6 and LFP are intergranular contacts poor, cannot be formed efficiently
Conductive network so that specific discharge capacity of the conventional phosphoric acid iron lithium electrode prepared by comparative experiments example 2 under 1 C current density
Only 128.1 mAh g-1, and the capacity retention ratio under the high current density of 7 C is only 25%(as shown in Fig. 13), table
Reveal poor multiplying power property.
Comparative analysis
The present invention by introduce two or more nano-carbon material and conductive agent to supercapacitor porous carbon electrodes
Material or lithium ion battery electrode material carry out composite modified.Gained supercapacitor or lithium ion battery novel three-dimensional nanometer
In combination electrode material, nano-carbon material equably wind (cladding) porous carbon materials particle surface (attached drawing 1) or lithium from
The surface (attached drawing 11-a, 11-b, 11-c) of sub- battery electrode material particle, and connect with conventional conductive agent particle, it is collectively formed
Good three-dimensional conductive network.With without the composite modified supercapacitor of nano-carbon material with conventional electrode materials (attached drawing 2)
Or lithium ion battery is compared with conventional electrode materials (attached drawing 11-d), nano-carbon material composite modification technology of the invention can be abundant
The synergistic effect for playing a variety of nano-carbon materials and conventional conductive agent greatly improves leading for supercapacitor porous carbon electrodes
The electrically electric conductivity (attached drawing 12) and multiplying power of (attached drawing 3,4) and high rate performance (attached drawing 5,6) or electrode material for lithium ion cell
Performance (attached drawing 13), to greatly improve the super capacitor based on high-performance novel three-dimensional manometer combination electrode material of the invention
The power characteristic of device or lithium ion battery, power density and service life cycle (attached drawing 9,10).
In addition, the present invention is more to supercapacitor use by the nano-carbon material and conductive agent for introducing two or more
Hole carbon electrode material or lithium ion battery electrode material carry out composite modified.Give full play to nano-carbon material and conventional conductive agent
Synergistic effect and form effect, by carbon nanotube, graphene in supercapacitor porous carbon electrode material or lithium ion
The uniform winding (cladding) on battery electrode material surface；Carbon nanotube, carbon nano-fiber are in supercapacitor porous carbon electrodes
Connection between material or the particle of lithium ion battery electrode material；Conventional conductive agent particle is in supercapacitor porous carbon electricity
Effective filling between pole material or the particle of lithium ion battery electrode material, so that three-dimensional manometer combination electrode material of the invention
Material more closely, packing density it is high, so as to improve super based on high-performance novel three-dimensional manometer combination electrode material of the invention
The energy density of grade capacitor or lithium ion battery.
To sum up, electrochemical energy storage of the invention three-dimensional manometer combination electrode material packing density height, good conductivity,
Multiplying power property and electrochemical stability are excellent, and the electrochemical energy storage of the invention system of three-dimensional manometer combination electrode material
It is Preparation Method simple process, environmentally protective, low in cost, it is suitable for industrialized production.
Claims (10)
1. a kind of electrochemical energy storage three-dimensional manometer combination electrode material, it is characterised in that by two or more nanometer
Carbon material, conductive agent, binder and supercapacitor porous carbon electrode material or lithium ion battery electrode material are combined institute
State three-dimensional manometer combination electrode material.
2. electrochemical energy storage three-dimensional manometer combination electrode material according to claim 1, it is characterised in that described three
Tie up each component ratio by mass percentage in nanometer combined electrode material are as follows: nano-carbon material 0.01~10%, conductive agent 1~
20%, binder 1~20%, supercapacitor porous carbon electrode material 50~97.99% or lithium ion battery electrode material 50~
97.99%。
3. electrochemical energy storage according to claim 1 or claim 2 three-dimensional manometer combination electrode material, it is characterised in that described
Nano-carbon material is carbon nanotube, graphene, two or more in carbon nano-fiber；The carbon nanotube is single wall carbon
Nanotube and/or multi-walled carbon nanotube, the graphene are single-layer graphene and/or multi-layer graphene.
4. electrochemical energy storage according to claim 1 or claim 2 three-dimensional manometer combination electrode material, it is characterised in that described
Conductive agent is one of carbon black, acetylene black, electrically conductive graphite, conductive Carbon fibe or more than one combinations；The binder is carboxylic
Sodium carboxymethylcellulose pyce, butadiene-styrene rubber, butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyvinyl alcohol, acroleic acid resin
One of or more than one combination.
5. electrochemical energy storage according to claim 1 or claim 2 three-dimensional manometer combination electrode material, it is characterised in that described super
Grade capacitor porous carbon electrode material is active powdered carbon, active carbon cloth, activated carbon fibre, carbon aerogels, porous graphite, porous hard
One of carbon, mesoporous carbon or more than one combinations.
6. electrochemical energy storage according to claim 1 or claim 2 three-dimensional manometer combination electrode material, it is characterised in that described
The positive electrode of lithium ion battery electrode material is one in LiFePO4, cobalt acid lithium, LiMn2O4, nickel ion doped or ternary material
Kind or more than one combinations；Negative electrode material be graphite, hard carbon, soft carbon, mesocarbon microspheres, silicon, silicon/carbon composite, titanium
One of sour lithium or more than one combinations.
7. electrochemical energy storage three-dimensional manometer combination electrode material according to claim 1, it is characterised in that the electricity
Pole material shape is button wafer type, and column type is winding-type, stacked square or stacked abnormal shape.
8. a kind of three wiener of supercapacitor for preparing three-dimensional manometer combination electrode material described in claim 1~7 any one
Rice method for preparing composite electrode, including graphite oxide preparation, the preparation of graphene in-stiu coating porous carbon materials, carbon nano-fiber point
Dispersion liquid preparation, supercapacitor three-dimensional manometer combination electrode preparation step, it is characterised in that specifically include:
A, prepared by graphite oxide: referring to improved Hummers method, with the potassium permanganate and body for being 3:1 with crystalline flake graphite mass ratio
Product/mass ratio is that the concentrated sulfuric acid of 23 ml:1 g aoxidizes the crystalline flake graphite of certain mass, is removed with hydrogen-peroxide reduction surplus
Remaining oxidant, separating, washing, drying, is prepared oxidation graphite solid；
B, graphene in-stiu coating porous carbon materials prepare: the graphite oxide that the step A is prepared in aqueous solution into
Row ultrasound removing forms graphene oxide and carries out in-stiu coating to porous carbon simultaneously, then with hydrazine hydrate to gained graphite oxide
Alkene is restored, and the porous carbon materials of redox graphene in-stiu coating are prepared in separating, washing, drying；
C, prepared by carbon nanofiber dispersion liquid: being acidified with the concentrated sulfuric acid/concentrated nitric acid mixed acid to carbon nano-fiber, table is added
Face activating agent is acidified carbon nano-fiber ultrasonic disperse in aqueous solution to gained, and carbon nanofiber dispersion liquid is prepared；
D, prepared by supercapacitor three-dimensional manometer combination electrode: in mass ratio by 50~97.99% supercapacitor porous carbon electrodes
Material, 0.01~10% nano-carbon material, 1~20% conductive agent, 1~20% binder and 0.01~10% step C made from carbon
Nanofiber dispersion liquid；Or redox graphene in-stiu coating made from the step B in mass ratio by 50~97.99% is porous
Carbon material, 1~20% conductive agent, 1~20% binder and 0.01~10% step C made from carbon nanofiber dispersion liquid or
0.01~10% nano-carbon material is added in aqueous solution together, and electrode slurry is formed after vacuum high-speed stirred, then by electrode slurry
Material is uniformly coated on collection liquid surface, and supercapacitor three-dimensional manometer combination electrode is made after drying, roll-in, cutting.
9. supercapacitor three-dimensional manometer method for preparing composite electrode according to claim 8, it is characterised in that the table
Face activating agent is in lauryl sodium sulfate, neopelex, dodecyl sodium sulfate or polyvinylpyrrolidone
It is one or more kinds of；The aqueous solution is ultrapure water, deionized water or distilled water.
10. a kind of three wiener of lithium ion battery for preparing three-dimensional manometer combination electrode material described in claim 1~7 any one
Rice method for preparing composite electrode, including the preparation of graphene in-stiu coating lithium ion battery electrode material, graphene oxide dispersion
Preparation, the preparation of redox graphene dispersion liquid, lithium ion battery three-dimensional manometer combination electrode preparation step, it is characterised in that tool
Body includes:
A, graphene in-stiu coating lithium ion battery electrode material prepare: graphite oxide is carried out in ultrapure water ultrasound removing,
Gained graphene oxide is restored with hydrazine hydrate and in-stiu coating is carried out to lithium ion battery electrode material, separated, washed
It washs, dry, redox graphene in-stiu coating lithium ion battery electrode material is prepared；
B, prepared by graphene oxide dispersion: the graphite oxide is carried out to ultrasonic removing, dispersion in N-Methyl pyrrolidone,
Graphene oxide dispersion is prepared；
C, prepared by redox graphene dispersion liquid: graphite oxide is subjected to high temperature reduction under the atmosphere of nitrogen or argon gas, with
N-Methyl pyrrolidone is solution, carries out ultrasonic removing to resulting redox graphene and disperses, oxygen reduction is prepared
Graphite alkene dispersion liquid；
D, lithium ion battery three-dimensional manometer combination electrode prepare: in mass ratio by 50~97.99% lithium ion battery electrode materials,
0.01~10% nano-carbon material, 1~20% conductive agent, 1~20% binder and 0.01~10% step B made from graphite oxide
Alkene dispersion liquid or 0.01~10% step C made from redox graphene dispersion liquid；Or in mass ratio by 50~97.99%
Graphene in-stiu coating lithium ion battery electrode material made from step A, 0.01~10% nano-carbon material, 1~20% conductive agent,
1~20% binder is added together in N-Methyl pyrrolidone solution, and electrode slurry is formed after vacuum high-speed stirred, then will
Electrode slurry is uniformly coated on collection liquid surface, and lithium ion battery three-dimensional manometer compound electric is made after drying, roll-in, cutting
Pole.
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