CN104882611B - A kind of Anodic electrode, energy storage device comprising the anode electrode and preparation method thereof - Google Patents

A kind of Anodic electrode, energy storage device comprising the anode electrode and preparation method thereof Download PDF

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CN104882611B
CN104882611B CN201510153392.XA CN201510153392A CN104882611B CN 104882611 B CN104882611 B CN 104882611B CN 201510153392 A CN201510153392 A CN 201510153392A CN 104882611 B CN104882611 B CN 104882611B
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graphene
porous graphene
anode
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anodic
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CN104882611A (en
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杨玉洁
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Guangdong Candle Light New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention belongs to technical field of energy storage, more particularly to a kind of electrochemical energy storing device anode:The anode pole piece includes anodic coating and base material, and the anodic coating includes anode active material, bonding agent and conductive agent, a diameter of a of the active material, and the conductive agent at least contains graphene;Characterized in that, the graphene is porous graphene, pitch of holes b, and b≤10a.The electrochemical energy storing device anode of this structure, due to having used porous graphene as conductive agent, smaller to the diffusional resistance of ion perpendicular to graphene planes direction, therefore there is more excellent chemical property.

Description

A kind of Anodic electrode, the energy storage device comprising the anode electrode and its preparation Method
Technical field
The invention belongs to technical field of energy storage, more particularly to a kind of Anodic electrode, the storage comprising the anode electrode Energy device and preparation method thereof.
Background technology
Since 1991, carbon material creativeness applied to field of lithium ion battery, and brings the revolutionary change in the field Change --- efficiently and after the multiple discharge and recharge of carry out of safety, it is just widely applied to mobile phone, video camera, notebook electricity On brain and other portable electronics.Compared with traditional plumbic acid, Ni-Cd, MH-Ni battery, lithium ion battery has higher Than volume energy density, weight/power ratio energy density, more preferable environment friendly, smaller self discharge and longer cycle life Deng being 21st century preferable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
However as the raising of life taste, people propose higher demand for experience to mobile electrical appliance:Gentlier, more Thin, smaller, more longlasting, safer is that these experience representative several aspects, and more longlasting is wherein most important One of experience.This just proposes higher energy density demand to electrical storage device (battery), and selects performance is more excellent to lead Electric agent prepares battery, can significantly improve the performance of battery.
2004, strong K seas nurse of peace moral (Andre K.Geim) of Univ Manchester UK etc. used mechanical stripping Graphene (Graphene) is prepared in method first, has thus pulled open material preparation, the prelude of operational research.So-called graphite Alkene, refer to generally be made up of single or multiple lift graphite flake layer in a kind of plates of hexagonal annular arrangement between carbon atom, can be Two-dimensional space infinitely extends, it may be said that is proper two-dimensional structure material.It has that specific surface area is big, electrical and thermal conductivity The outstanding advantages such as energy is excellent, thermal coefficient of expansion is low:Specifically, high specific surface area (calculated value:2630m2/g);Height is led Electrically, carrier transport rate (200000cm2/V·s);High heat conductance (5000W/mK);High intensity, high Young's modulus (1100GPa), fracture strength (125GPa).Therefore it has pole in energy storage field, heat transfer field and Materials with High Strength field Big utilization prospect.
Specifically, because graphene has excellent electric conductivity, and the quality of itself is extremely light, therefore can be effective Conductive agent dosage is reduced, increases the content of active material in electrode, improves the energy density of battery;Battery can also be reduced simultaneously Internal resistance, the discharge voltage of battery is improved, reduce the heat production in charge and discharge process;Therefore graphene is lithium ion battery conductive agent One of ideal chose.However, the two-dimensional structure of graphene in itself, significantly limit lithium ion perpendicular to graphene film studio side Upward diffusion, so as to limit performance of the graphene as lithium ion battery conductive agent performance.
In view of this, it is necessory to develop a kind of new grapheme material, its structure will not hinder ion perpendicular to stone Transmission on black alkene lamella direction.
The content of the invention
It is an object of the invention to:In view of the shortcomings of the prior art, a kind of Anodic electrode provided:The anode Pole piece includes anodic coating and base material, and the anodic coating includes anode active material, bonding agent and conductive agent, the active matter The average diameter of matter is a, and the conductive agent at least contains graphene;The graphene is porous graphene, and average pitch of holes is B, and b≤10a.The electrochemical energy storing device anode of this structure, due to having used porous graphene as conductive agent, vertical It is smaller to the diffusional resistance of ion in graphene planes direction, therefore there is more excellent chemical property.
To achieve these goals, the present invention adopts the following technical scheme that:
A kind of Anodic electrode, including base material and the anodic coating being arranged on the base material, the anodic coating Including anode active material, bonding agent and conductive agent, the average diameter of the anode active material is a, and the conductive agent is at least Contain graphene;Characterized in that, the graphene is porous graphene, and the average distance between adjacent hole is (average Pitch of holes) it is b, and b≤10a.Average distance between the adjacent hole refers to the average distance between adjacent two bore edges, Referred to as be averaged pitch of holes.
As Anodic electrode of the present invention one kind improve, when the graphene sheet layer plane equivalent diameter D≤ During 10a, the graphene can be non-porous graphene;The graphene film layer plane equivalent diameter refers to put down graphene sheet layer When face area is converted into an area of a circle, the diameter of a circle.
One kind as Anodic electrode of the present invention is improved, and the anode active material is carbons material, alloy type At least one of material, metal oxide series material, metal nitride materials and carbon compound;The conductive agent can be with Contain at least one of conductive black, super conductive carbon, CNT, conductive carbon fibres peacekeeping Ketjen black.
One kind as Anodic electrode of the present invention is improved, and the thickness of the porous graphene is less than or equal to 350nm, and the slice plane equivalent diameter D of the porous graphene is more than or equal to 5nm;The quality of the graphene accounts for institute State the 0.05%~10% of anodic coating gross mass.
One kind as Anodic electrode of the present invention is improved, the average diameter d≤a in the hole of the porous graphene; Hole is shaped as circle, square, triangle, ellipse or polygon.
One kind as Anodic electrode of the present invention is improved, the diameter d≤0.1a in the hole of the porous graphene, institute The shape of stating the hole of porous graphene is identical, area equation, and the distance between adjacent hole is equal.
One kind as Anodic electrode of the present invention is improved, being averaged between the adjacent hole of the porous graphene Distance b≤2a.
One kind as Anodic electrode of the present invention is improved, 5nm≤a≤500um.
A kind of electrochemical energy storing device, including anode electrode of the present invention, the electrochemical energy storing device are plumbic acid It is any one in battery, Ni-MH battery, lithium ion battery, lithium-sulfur cell, sodium-ion battery, Zinc ion battery and ultracapacitor Kind.
It is main to include following step present invention additionally comprises a kind of preparation method of electrochemical energy storing device of the present invention Suddenly:
Step 1, the preparation of anode pole piece:By average diameter for a anode active material, at least containing porous graphene Conductive agent, bonding agent and solvent are well mixed, and (anode active material is graphite, silicon, Si-C composite material, lithium titanate Deng;Conductive agent position conductive black, super conductive carbon, CNT, Ketjen black, non-porous graphene etc.;Bonding agent includes gathering inclined fluorine Ethene, butadiene-styrene rubber, neopelex etc.;Solvent is water, N-methyl Topiramate Los oxazolidinone etc.), anode slurry is obtained, Afterwards coated on base material, anode pole piece is obtained after cold pressing, slitting, welding, wherein, the adjacent hole of the porous graphene it Between average distance be b, and b≤10a;
Step 2, the preparation of finished product battery core:The anode pole piece that step 1 is prepared assembles with cathode sheet, barrier film To naked battery core, finished product battery core is obtained after entering shell/enter bag, drying, fluid injection, standing, chemical conversion, shaping afterwards.
The beneficial effects of the present invention are:Different from traditional electrode, strict regulations of the present invention are as the more of conductive agent The hole size and pitch of holes of hole graphene sheet layer, i.e., it is no more than active material particle, pitch of holes not as conductive agent, its hole size More than 10 times of active substance particle size, the battery core for being prepared out has more preferable high rate charge-discharge performance.Because Graphene conductive agent with this structure, its obstruction to lithium ion diffusion in charge and discharge process can be effectively avoided to make With.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention Formula not limited to this.
Comparative example 1, the preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, afterwards according to stone Ink:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Conductive black (200nm)=94.7:1:2.3:2 relationship between quality is weighed, and addition is gone Stirring obtains anode slurry in ionized water, must coated on copper current collector, then after the processes such as cold pressing, slitting, welding, rubberizing It is standby to anode pole piece.
Battery assembles:It is cathode active material to select cobalt acid lithium, according to cathode capacities:Anode capacity=100:112 appearance Magnitude relation designs battery.According to above-mentioned capacity relationship configure cathode slurry and control coating quality, cold pressing afterwards, slitting, welding, Cathode sheet is obtained after rubberizing.Obtained cathode sheet, anode pole piece and barrier film are wound to obtain naked battery core, select aluminum plastic film Closedtop, side seal are carried out for packaging bag, drying afterwards, fluid injection, standing, chemical conversion, shaping, degasification obtain finished product lithium ion battery.
Comparative example 2, unlike comparative example 1, this comparative example comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um is conductive agent without hole graphene (thickness 3nm);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber: Graphene=96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated in copper On collector, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is identical with comparative example 1, is not repeating here.
Embodiment 1, unlike comparative example 2, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, hole it is a diameter of 0.1um (0.1a), pitch of holes are 10um (10a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphene= 96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated on copper current collector, Anode pole piece to be obtained after the processes such as cold pressing, slitting, welding, rubberizing standby again.
Remaining is identical with comparative example 2, is not repeating here.
Embodiment 2, as different from Example 1, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, hole it is a diameter of 0.1um (0.1a), pitch of holes are 2um (2a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphene= 96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated on copper current collector, Anode pole piece to be obtained after the processes such as cold pressing, slitting, welding, rubberizing standby again.
Remaining is same as Example 1, is not repeating here.
Embodiment 3, as different from Example 1, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, the average diameter in hole For 0.1um (0.1a), average pitch of holes is 0.4um (0.4a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Stone Black alkene=96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated in copper collection On fluid, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is same as Example 1, is not repeating here.
Embodiment 4, as different from Example 3, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, a diameter of 1um in hole (a), pitch of holes is 0.4um (0.4a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphene=96.2:1: 2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated on copper current collector, then passes through It is standby that anode pole piece is obtained after the processes such as cold pressing, slitting, welding, rubberizing.
Remaining is same as Example 3, is not repeating here.
Embodiment 5, as different from Example 3, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, the average diameter in hole For 0.02um (0.02a), average pitch of holes is 0.4um (0.4a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber: Graphene=96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated in copper On collector, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is same as Example 3, is not repeating here.
Embodiment 6, as different from Example 3, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 5nm silicon, and the plane equivalent diameter of lamella is 5nm porous graphene (thickness 0.3nm) is conductive agent, and the hole shape of the porous graphene is regular hexagon, hole it is equivalent A diameter of 1nm (0.2a), average pitch of holes is 1nm (0.2a);Afterwards according to silicon:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphite Alkene=94.2:1:2.3:2.5 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated in copper afflux On body, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is same as Example 3, is not repeating here.
Embodiment 7, as different from Example 3, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, hole it is a diameter of 0.1um (0.1a), pitch of holes are 0.4um (0.4a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphene: Super conductive carbon=94.7:1:2.3:0.05:1.95 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry Material, coated on copper current collector, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is same as Example 3, is not repeating here.
Embodiment 8, as different from Example 3, the present embodiment comprises the following steps:
The preparation of anode pole piece:Selection average grain diameter is active material for 1um graphite, and the plane equivalent diameter of lamella is 100um porous graphene (thickness 3nm) is conductive agent, and the hole shape of the porous graphene is circular hole, the average diameter in hole For 0.1um (0.1a), pitch of holes is 0.4um (0.4a);Afterwards according to graphite:Sodium carboxymethylcellulose:Butadiene-styrene rubber:Graphene =86.7:1:2.3:10 relationship between quality weighs, and adds stirring in deionized water and obtains anode slurry, coated in copper current collector On, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain anode pole piece standby.
Remaining is same as Example 3, is not repeating here.
It is prepared by embodiment 9, electrode slice:Selection average grain diameter is active material for 500um hard carbon, and the plane of lamella is equivalent A diameter of 200um porous graphene (thickness 100nm) is conductive agent, and the hole shape of the porous graphene is triangle, hole Equivalent diameter be 10um (0.02a), pitch of holes is 20um (0.04a);Afterwards according to hard carbon:Sodium carboxymethylcellulose:Butylbenzene Rubber:Graphene=96.2:1:2.3:0.5 relationship between quality weighs, and adds stirring in deionized water and obtains electrode slurry, applies On copper current collector, then after the processes such as cold pressing, slitting, welding, rubberizing to obtain pole piece standby.
Ultracapacitor assembles:By compatible above-mentioned electrode and barrier film lamination, enter shell, fluid injection afterwards, encapsulate and obtain Ultracapacitor.
Characterize and test:
Volume test:The lithium ion battery that comparative example 1,2 and embodiment 1-8 are prepared respectively carries out capacity survey Examination.Volume test is carried out to battery core by following flow in 35 DEG C of environment:Stand 3min;0.5C constant-current charges are to 4.2V, constant pressure Charge to 0.05C;Stand 3min;0.5C constant-current discharges obtain discharge capacity D0 first to 3.0V;3min is stood to complete to hold afterwards Examination is measured, acquired results are shown in Table 1.
The ultracapacitor of embodiment 9 is tested as follows:Battery core is held by following flow in 35 DEG C of environment Measure examination:Stand 3min;0.5C constant-current charges are to 1V;Stand 3min;0.5C constant-current discharges obtain discharge capacity D0 first to 0V; Stand 3min and complete volume test afterwards, acquired results are shown in Table 1.
Multiplying power is tested:The lithium ion battery that comparative example 1,2 and embodiment 1-8 are prepared respectively carries out multiplying power survey Examination.Battery core is subjected to multiplying power test in 35 DEG C of environment, flow is:Stand 3min;0.5C constant-current charges are to 4.2V, constant-voltage charge To 0.05C;Stand 3min;0.2C constant-current discharges obtain discharge capacity D0 first to 3.0V.Stand 3min;0.5C constant-current charges are extremely 4.2V, constant-voltage charge to 0.05C;Stand 3min;2C constant-current discharges obtain discharge capacity D1 first to 3.0V.High rate performance Rate =D1/D0, acquired results are shown in Table 1.
The ultracapacitor of embodiment 9 is tested as follows:Battery core is subjected to multiplying power test, flow in 35 DEG C of environment For:Stand 3min;0.5C constant-current charges are to 1V;Stand 3min;0.5C constant-current discharges obtain discharge capacity D0 first to 0V.Stand 3min;0.5C constant-current charges are to 1V;Stand 3min;20C constant-current discharges obtain discharge capacity D1 first to 0V.High rate performance Rate =D1/D0, acquired results are shown in Table 1.
Analytical table 1, comparative examples 1 and comparative example 2 can be obtained, and battery appearance can be significantly improved when graphene is as conductive agent Amount, but can reduce the high rate performance of battery, this be due to the graphene film studio of two-dimensional structure limit lithium ion perpendicular to Transmission on graphene planes, cause the reduction of battery high rate performance.Comparative examples 2, embodiment 1-3 are it can be found that work as conduct When the graphene of conductive agent is porous graphene, it can significantly improve the high rate performance of battery, particularly work as porous graphene Pitch of holes in 2a or following, the high rate performance of battery be substantially better than conductive black (comparative example 1) as conductive agent lithium from Sub- battery, this is due to the pore space structure on graphene sheet layer, eliminates the limitation that graphene two dimensional surface spreads to lithium ion Effect, so as to improve the high rate performance of battery.Comparative example 3-5 can be obtained, the multiplying power of the bore dia of loose structure to battery core Performance impact is smaller.
The electrical property table of the electrochemical energy storing device of table 1, comparative example and embodiment
It can be obtained by embodiment 9, the invention is also practically applicable to ultracapacitor field, illustrates that the present invention has universality.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention Form any restrictions.

Claims (9)

1. a kind of Anodic electrode, including base material and the anodic coating being arranged on the base material, the anodic coating bag Anode active material, bonding agent and conductive agent are included, the average diameter of the anode active material is a, and the conductive agent at least contains There is graphene;Characterized in that, the graphene is porous graphene, and the average distance between adjacent hole is b, and b ≤10a。
A kind of 2. Anodic electrode described in claim 1, it is characterised in that the anode active material be carbon material, At least one of alloy material, metal oxide materials, metal nitride materials and carbon compound;The conductive agent also contains At least one of conductive black, super conductive carbon, CNT, conductive carbon fibres peacekeeping Ketjen black.
A kind of 3. Anodic electrode described in claim 1, it is characterised in that the thickness of the porous graphene be less than or Slice plane equivalent diameter D equal to 350nm, and the porous graphene is more than or equal to 5nm;The quality of the graphene Account for the 0.05%~10% of the gross mass of the anodic coating.
4. the Anodic electrode described in a kind of claim 1, it is characterised in that being averaged for the hole of the porous graphene is straight Footpath d≤a;Hole is shaped as circle, square, triangle, ellipse.
A kind of 5. Anodic electrode described in claim 1, it is characterised in that the diameter d in the hole of the porous graphene ≤ 0.1a, the shape in the hole of the porous graphene is identical, area equation, and the distance between adjacent hole is equal.
A kind of 6. Anodic electrode described in claim 1, it is characterised in that the adjacent hole of the porous graphene it Between average distance b≤2a.
A kind of 7. Anodic electrode described in claim 1, it is characterised in that 5nm≤a≤500 μm.
8. a kind of electrochemical energy storing device, including the anode electrode described in any one of claim 1 to 7, the electrochemical energy storage Device is lead-acid battery, Ni-MH battery, lithium ion battery, lithium-sulfur cell, sodium-ion battery, Zinc ion battery and ultracapacitor In any one.
9. the preparation method of the electrochemical energy storing device described in a kind of claim 8, it is characterised in that main to include following step Suddenly:
Step 1, the preparation of anode pole piece:It is a anode active material, at least conduction containing porous graphene by average diameter Agent, bonding agent and solvent are well mixed, and obtain anode slurry, afterwards coated on base material, after cold pressing, slitting, welding Anode pole piece is obtained, wherein, the average distance between the adjacent hole of the porous graphene is b, and b≤10a;
Step 2, prepared by finished product battery core:The anode pole piece that step 1 is prepared assembles to obtain naked electricity with cathode sheet, barrier film Core, finished product battery core is obtained after entering shell/enter bag, drying, fluid injection, standing, chemical conversion, shaping afterwards.
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