CN105322178B - A kind of electrochemical cell electrode, electrochemical cell containing the electrode and preparation method thereof - Google Patents

A kind of electrochemical cell electrode, electrochemical cell containing the electrode and preparation method thereof Download PDF

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CN105322178B
CN105322178B CN201510676246.5A CN201510676246A CN105322178B CN 105322178 B CN105322178 B CN 105322178B CN 201510676246 A CN201510676246 A CN 201510676246A CN 105322178 B CN105322178 B CN 105322178B
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graphene
collector
electrochemical cell
buffer layer
layer
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CN105322178A (en
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杨玉洁
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Guangdong Candle Light New Energy Technology Co Ltd
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Guangdong Candle Light New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/64Carriers or collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/621Binders
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • 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

Abstract

The invention belongs to field of preparation of graphene, in particular to a kind of electrochemical cell pole piece, including collector and active material layer is provided with buffer layer between the collector and the active material layer, the buffer layer with a thickness of 0.336nm~4 μm;The buffer layer contains bonding agent and conductive agent, and the conductive agent includes graphene, and the angle between the slice plane of the graphene and the plane of the collector is θ, and the quality of the graphene of θ < 45 ° accounts for the ratio of graphene total amount more than or equal to 50%.At this point, graphene tends to be parallel to collector arrangement, shared by thickness it is smaller, therefore the buffer layer thickness of inert matter component is smaller, and battery has higher energy density.

Description

A kind of electrochemical cell electrode, the electrochemical cell containing the electrode and its preparation Method
Technical field
The invention belongs to field of electrochemical batteries, in particular to a kind of electrochemical cell electrode, the electrification containing the electrode Learn battery and preparation method thereof.
Background technique
Into after 21 century, various electronic device products such as mobile phone, notebook, wearable device etc. emerge one after another, pole The big life for enriching users;Meanwhile electric car and all kinds of energy-accumulating power stations also rapid rudiment, hair like the mushrooms after rain Exhibition is grown.The above high-tech product, with a common trait: the battery of high-performance, low cost being needed to serve as energy storage component.
Existing battery mainly once battery and secondary cell two major classes;So-called one-shot battery can not charge repeatedly Battery, mainly include carbon zinc battery, alkaline battery, paste type zinc-manganese battery, cardboard Zn-Mg battery, alkaline zinc-managanese dioxide cell, button Battery (button zinc-silver oxide cell, button type lithium-manganese battery, button Zn-Mg battery), zinc-air battery, a lithium-manganese cell etc., mercury electricity Pond;So-called secondary cell, i.e. rechargeable battery mainly include secondary alkaline zinc manganese cell, Ni-Cd nickel-cadmium, nickel hydride charging electricity Pond, lithium rechargeable batteries, lead-acid battery, solar battery.Lead-acid accumulator can be divided into: open type lead-acid accumulator, totally-enclosed lead Acid accumulator.And from outer packing angle analysis, existing battery is broadly divided into flexible-packed battery and hard shell battery pack, due to Soft Roll Packed battery packaging film thickness itself is small, and plasticity is big, is widely applied in all kinds of high-grade one-shot batteries and secondary cell.
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 safer, more longlasting is wherein One of most important experience, this just proposes higher safety and energy density demand to electrical storage device (battery);More using impedance Low electrode slice, the higher electrode material of energy density be solve battery core security performance, improve battery core energy density have efficacious prescriptions Method.
For existing electrode material, often energy density is higher, and charge and discharge cubical expansivity is bigger, therefore fills The probability for causing finished product battery core electrode coating to fall off in discharge process is higher, so as to cause cycle performance of battery variation.Meanwhile being Make the energy force density of battery entirety high, inert matter component proportion, thickness must be just compressed to minimum in battery; And graphene (Graphene) sheet layer material thickness direction is most thin in current material.
In view of this, not only resistivity is low, can improve electricity it is necessory to develop a kind of new electrochemical cell electrode The cycle performance in pond also has inactive material layer thin as far as possible.
Summary of the invention
It is an object of the invention to: in view of the deficiencies of the prior art, and a kind of electrochemical cell pole piece provided, including collection Fluid and active material layer are provided with buffer layer, the thickness of the buffer layer between the collector and the active material layer For 0.336nm~4 μm;The buffer layer contains bonding agent and conductive agent, and the conductive agent includes graphene, the graphene Angle between slice plane and the plane of the collector is θ, and the quality of the graphene of θ < 45 ° accounts for the ratio of graphene total amount Example is greater than or equal to 50%.At this point, graphene tends to be parallel to collector arrangement, shared by thickness it is smaller therefore non-live Property substance component buffer layer thickness it is smaller, battery have higher energy density.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of electrochemical cell pole piece, including collector and active material layer, the collector and the active material layer Between be provided with buffer layer, the buffer layer with a thickness of 0.336nm~4 μm;The buffer layer contains bonding agent and conductive agent, The conductive agent includes graphene, and the angle between the slice plane of the graphene and the plane of the collector is θ, and θ < The ratio that the quality of 45 ° of graphene accounts for graphene total amount is greater than or equal to 50%.θ < 45 ° are that graphene sheet layer tends to put down Row is arranged in collector;And " ratio that the quality of the graphene of θ < 45 ° accounts for graphene total amount is greater than or equal to 50% " is more Number graphene all tends to be parallel to collector arrangement;Since graphene is in each dimension, thickness dimension is minimum, when it is parallel It is that the buffer layer thickness is lower, therefore the buffer layer thickness of inert matter component is smaller in collector arrangement, battery has more High energy density.
As a kind of a kind of improvement of electrochemical cell pole piece of the present invention, the buffer layer with a thickness of the μ of 0.336nm~2 M, preferably 1nm~1 μm, buffer layer thickness is smaller, and thickness shared by inert matter component is lower, and battery energy density is higher;Institute The ratio for the quality that the quality for stating bonding agent accounts for the buffer layer is 0.5%~10%, when bonding agent ratio is too low, and buffer layer holds It is easy to fall off, and buffering effect is bad;When bonding agent ratio is excessively high, the electric conductivity of this layer will affect;The quality of the conductive agent The ratio for accounting for the quality of the buffer layer is 90%~99.5%, and conductive agent ratio is too low, and buffer layer resistance is high, and impedance is big;It leads Electric agent ratio is excessively high, is easy to fall off, influences buffering effect.
As a kind of a kind of improvement of electrochemical cell pole piece of the present invention, the bonding agent be Kynoar (PVDF), At least one of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR);The conductive agent further includes conductive black, super Conductive carbon, carbon nanotube, conductive at least one of Carbon fibe and Ketjen black;The quality of the graphene accounts for the conductive agent The ratio of gross mass is 10%~100%.
As a kind of a kind of improvement of electrochemical cell pole piece of the present invention, the graphene with a thickness of 0.336nm~ 100nm, the lamella of the graphene planar dimension (i.e. the equivalent diameter of graphene film layer plane, " equivalent diameter " be with The equal diameter of a circle of the area of plane) it is greater than or equal to 10nm, when graphene sheet layer is smaller, it is difficult to control it and be parallel to collector Arrangement, therefore the graphene better effect of bigger lamella;The graphene is graphene oxide, graphene and modified graphene (in order to increase response of the graphene sheet layer to magnetic field, modified graphene can for it is compound on graphene sheet layer/be grafted with easy magnetic At least one of change element, such as iron, steel, cobalt, nickel element).
As a kind of a kind of improvement of electrochemical cell pole piece of the present invention, (θ is smaller, illustrates graphene film for angle theta≤30 ° Layer is more likely to be parallel to collector arrangement) graphene quality account for graphene total amount ratio be greater than or equal to 50% or/ With the quality of the graphene of angle theta≤45 ° account for graphene total amount ratio be greater than or equal to 70% (θ is smaller, ratio is higher, In the case where identical graphene, obtained buffer layer can be made thinner).
As a kind of a kind of improvement of electrochemical cell pole piece of the present invention, the electrochemical cell includes nickel-metal hydride battery, nickel Cadmium cell, lead-acid battery, lithium ion battery, capacitor, Zinc ion battery, lithium-sulfur cell or sodium-ion battery;The pole piece packet Include positive plate or/and negative electrode tab.
The invention also includes a kind of electrochemical cell, including positive plate, negative electrode tab, isolation film, electrolyte and outer packing, institutes It states positive plate or/and the negative electrode tab is selected from electrode slice of the present invention.
The invention also includes a kind of preparation methods of electrochemical cell, mainly include the following steps:
Step 1: electrode slice preparation: the conductive agent containing graphene, bonding agent and solvent being mixed, solid content is configured to Slurry less than or equal to 40%, applies on a current collector later, and applies external force, so that the slice plane and afflux of graphene Angle theta≤45 ° between body plane obtain the collector containing bottom layer treatment layer after dry;Active material will be contained later Slurry be arranged in the surface of bottom layer treatment layer, it is stand-by to obtain electrode slice after drying;When slurry solid content is low, same glue amount Under, viscosity is smaller, it is more advantageous to the movement of graphene sheet layer, and potential energy is minimum when the graphene of sheet is laid on collector, Itself is in most stable state, is easy to keep tiled state;
Step 2: the preparation of finished product electrochemical cell: after pole piece cold pressing that step 1 is obtained, slitting, welding, with to electrode, Isolation film assembles to obtain naked battery core, enters shell/enter bag later, drying, fluid injection, chemical conversion, shaping obtain finished product electrochemical cell.
As a kind of improvement of electrochemical cell preparation method of the present invention, the solid content of slurry described in step 1 be less than or Equal to 6% (when solid content is lower, slurry viscosity is smaller, and graphene is easier to be laid on collector), applying external force is to apply Angle between collector is greater than or equal to 45 ° of magnetic field, and application time is before slurry is dry;The drying is freeze-drying Or heat drying.
As a kind of improvement of electrochemical cell preparation method of the present invention, step 1 prepares the afflux containing bottom layer treatment layer When body, also use CVD method in one layer of graphene of growth on collector as buffer layer.
The beneficial effects of the present invention are:
Firstly, graphene itself has excellent electric conductivity, the conductive agent as conductive buffer layer can be significantly reduced Battery impedance;
Secondly, graphene tends to be parallel to collector arrangement, shared by thickness it is smaller, therefore inert matter component Buffer layer thickness it is smaller, battery have higher energy density;
Finally, having selected the slurry that solid content is low, viscosity is low in preparation process, it is more advantageous to the movement of graphene sheet layer, And the graphene of sheet when being laid on collector potential energy it is minimum, itself be in most stable state, be easy to keep tiled state.
Specific embodiment
The present invention and its advantages are described in detail With reference to embodiment, but embodiment party of the invention Formula is without being limited thereto.
Comparative example, the preparation of negative current collector buffer layer: selecting conductive black for conductive agent, and PVDF is bonding agent (mass ratio It for 95:5), prepares and obtains the slurry that solid content is 40%, be coated on copper current collector later, obtain containing with a thickness of 2 μm of bufferings The collector of layer;
Negative electrode tab preparation: select mass ratio is the silicon of 1:9, graphite mixing material as active material, prepares and obtains cathode Slurry is coated on above-mentioned collection liquid surface later, it is stand-by to obtain negative electricity pole piece;
The preparation of finished product electrochemical cell: it after above-mentioned cathode cold pressing, slitting, welding, winds to obtain with anode, isolation film naked Battery core selects aluminum plastic film for packaging bag later, and progress closedtop, side seal, drying, fluid injection, chemical conversion, shaping obtain finished product electrochemistry electricity Pond.
Embodiment 1, unlike comparative example, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: the graphene for selecting lamellar spacing to be 1 μm for 1nm, planar dimension is used as conductive Agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later, After slurry coating after on collector, apply magnetic field until the solidification of diaphragm spreading mass, control magnetic field angle, power and coating When tape running speed so that about 80% graphene sheet layer and the angle of collector are 30 ° or so, thus obtain containing with a thickness of The collector of 1 μm of buffer layer;
Remaining is identical as comparative example, is not repeating here.
Embodiment 2, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: the graphene for selecting lamellar spacing to be 1 μm for 1nm, planar dimension is used as conductive Agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later, After slurry coating after on collector, apply magnetic field until the solidification of diaphragm spreading mass, control magnetic field angle, power and coating When tape running speed so that about 50% graphene sheet layer and the angle of collector are 44 ° or so, thus obtain containing with a thickness of The collector of 1 μm of buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 3, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: select lamellar spacing for 1nm, planar dimension is 1 μm, graphene is as conduction Agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later, After slurry coating after on collector, apply magnetic field until the solidification of diaphragm spreading mass, control magnetic field angle, power and coating When tape running speed so that about 70% graphene sheet layer and the angle of collector are 20 ° or so, thus obtain containing with a thickness of The collector of 1 μm of buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 4, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: select lamellar spacing for 1nm, planar dimension is 0.4 μm, graphene conduct is led Electric agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later On, after slurry coating after on collector, apply magnetic field until diaphragm spreading mass solidification until, control magnetic field angle, power and Tape running speed when coating, so that about 90% graphene sheet layer and the angle of collector are 10 ° or so, to obtain containing thickness Degree is the collector of 500nm buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 5, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: select lamellar spacing for 1nm, planar dimension is 0.2 μm, graphene conduct is led Electric agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later On, after slurry coating after on collector, apply magnetic field until diaphragm spreading mass solidification until, control magnetic field angle, power and Tape running speed when coating, so that about 90% graphene sheet layer and the angle of collector are 5 ° or so, to obtain containing thickness Degree is the collector of 100nm buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 6, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: select lamellar spacing for 1nm, planar dimension is 0.1 μm, graphene conduct is led Electric agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on copper current collector later On, after slurry coating after on collector, apply magnetic field until diaphragm spreading mass solidification until, control magnetic field angle, power and Tape running speed when coating, so that about 95% graphene sheet layer and the angle of collector are 0 ° or so, to obtain containing thickness Degree is the collector of 10nm buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 7, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: to select lamellar spacing for 100nm, planar dimension be 20 μm, graphene and is led Electric carbon black (partial size is 1 μm) (mass ratio 1:9) is used as conductive agent, and PVDF is bonding agent (mass ratio 99.5:0.5), is prepared The slurry that solid content is 40% is obtained, later coated on copper current collector, after slurry coating after on collector, it is straight to apply magnetic field Until the solidification of diaphragm spreading mass, tape running speed when magnetic field angle, power and coating is controlled, so that about 90% graphene film The angle of layer and collector is 10 ° or so, to obtain containing the collector with a thickness of 4 μm of buffer layers;
Remaining is same as Example 1, is not repeating here.
Embodiment 8, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: to select lamellar spacing for 10nm, planar dimension be 10 μm, graphene and conduction Carbon black (partial size is 1 μm) (mass ratio 5:5) is used as conductive agent, and PVDF is bonding agent (mass ratio 97:3), and preparation is consolidated The slurry that content is 15% after slurry coating after on collector, applies magnetic field until diaphragm later coated on copper current collector Until spreading mass solidifies, tape running speed when magnetic field angle, power and coating is controlled, so that about 90% graphene sheet layer and collection The angle of fluid is 10 ° or so, to obtain containing the collector with a thickness of 2 μm of buffer layers;
Remaining is same as Example 1, is not repeating here.
Embodiment 9, unlike the first embodiment, the present embodiment includes the following steps:
Negative current collector buffer layer preparation: select lamellar spacing for 2nm, planar dimension be 5 μm modified graphene (this changes Property graphene on be grafted with nickel element, content 0.5%) as conductive agent, PVDF is bonding agent (mass ratio 90:10), is matched The slurry that solid content is 6% is made, later coated on copper current collector, after slurry coating after on collector, applies magnetic field Until the solidification of diaphragm spreading mass, tape running speed when magnetic field angle, power and coating is controlled, so that about 90% graphene The angle of lamella and collector is 10 ° or so, to obtain containing the collector with a thickness of 500nm buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 10, unlike the first embodiment, the present embodiment includes the following steps:
Negative current collector buffer layer preparation: select lamellar spacing for 4nm, planar dimension be 5 μm modified graphene (this changes Property graphene on be grafted with cobalt element, content 0.5%) as conductive agent, PVDF is bonding agent (mass ratio 90:10), is matched The slurry that solid content is 6% is made, later coated on copper current collector, after slurry coating after on collector, applies magnetic field Until the solidification of diaphragm spreading mass, tape running speed when magnetic field angle, power and coating is controlled, so that about 90% graphene The angle of lamella and collector is 10 ° or so, to obtain containing the collector with a thickness of 500nm buffer layer;
Remaining is same as Example 1, is not repeating here.
Embodiment 11, unlike the first embodiment, the present embodiment includes the following steps:
The preparation of negative current collector buffer layer: using CVD method, grows one layer of graphene sheet layer in copper foil surface, is buffered Layer is stand-by with a thickness of 0.336 μm of buffer layer collector;
Remaining is same as Example 1, is not repeating here.
Embodiment 12, unlike 4, the present embodiment includes the following steps:
The preparation of plus plate current-collecting body buffer layer: select lamellar spacing for 3nm, planar dimension is 0.4 μm, graphene conduct is led Electric agent, PVDF are bonding agent (mass ratio 95:5), prepare and obtain the slurry that solid content is 3%, are coated on aluminium collector later On, after slurry coating after on collector, apply magnetic field until diaphragm spreading mass solidification until, control magnetic field angle, power and Tape running speed when coating, so that about 90% graphene sheet layer and the angle of collector are 10 ° or so, to obtain containing thickness Degree is the collector of 500nm buffer layer;
Positive plate preparation: selecting cobalt acid lithium for active material, and preparation obtains anode sizing agent, is coated on above-mentioned collector later It is stand-by to obtain anode electrode piece for surface;
The preparation of finished product electrochemical cell: it after above-mentioned positive cold pressing, slitting, welding, winds to obtain with cathode, isolation film naked Battery core selects aluminum plastic film for packaging bag later, and progress closedtop, side seal, drying, fluid injection, chemical conversion, shaping obtain finished product electrochemistry electricity Pond.
Remaining is same as Example 4, is not repeating here.
Characterization and test:
500 weeks loop tests: it is recycled in 25 DEG C of environment by battery core of the following process to each embodiment and comparative example Test: 3min is stood;0.5C constant-current charge is to 4.2V, constant-voltage charge to 0.05C;Stand 3min;0.5C constant-current discharge is to 3.0V Obtain discharge capacity D0 for the first time;Stand 3min;Above-mentioned test 499 weeks is repeated later, obtains capacity D499, then is followed within battery core 500 weeks Capacity retention ratio is D499/D0 after ring, the results are shown in Table 1;
DC impedance (IMP) test: it is carried out in 25 DEG C of environment by battery core of the following process to each embodiment and comparative example DC impedance (IMP) test: 3min is stood;0.5C constant-current charge is to 3.85V, constant-voltage charge to 0.05C;Stand 3min;Later DC impedance test is carried out using electrochemical workstation, the DC internal resistance of battery core is obtained, is shown in Table 1;
It can be obtained by table 1, the present invention can significantly improve the cycle performance of battery, while reduce the internal resistance of battery, therefore energy Thermal discharge when battery charging and discharging is enough reduced, the security performance of battery is improved;Meanwhile buffer layer thickness of the invention is very small, I.e. the thickness of inert matter component is very small in electrode, therefore obtained battery has higher energy density.
The electrical property table of the electrochemical energy storing device of table 1, comparative example and embodiment
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention Constitute any restrictions.

Claims (9)

1. a kind of electrochemical cell, including positive plate, negative electrode tab, isolation film, electrolyte and outer packing, which is characterized in that described Positive plate or/and the negative electrode tab include collector and active material layer, are set between the collector and the active material layer Be equipped with buffer layer, the buffer layer with a thickness of 0.336nm~4 μm;The buffer layer contains bonding agent and conductive agent, described to lead Electric agent includes graphene, and the angle between the slice plane of the graphene and the length and wide place plane of the collector is θ, And the quality of 45 ° of θ < of graphene accounts for the ratio of graphene total amount more than or equal to 50%;The graphene with a thickness of The size of 0.336nm~100nm, the slice plane of the graphene are greater than or equal to 10nm;The ruler of the slice plane of graphene The equivalent diameter of very little i.e. graphene film layer plane, equivalent diameter are the diameter of a circle equal with the area of plane;
Preparation method mainly includes the following steps:
Step 1: electrode slice preparation: the conductive agent containing graphene, bonding agent and solvent being mixed, solid content is configured to and is less than Or the slurry equal to 40%, it applies on a current collector later, and apply external force, so that the slice plane of graphene and collector Angle theta≤45 ° between the plane of long and wide place obtain the collector containing bottom layer treatment layer after dry;It will contain later The slurry of active material is arranged in the surface of bottom layer treatment layer, and it is stand-by to obtain electrode slice after drying;
Step 2: the preparation of finished product electrochemical cell: after pole piece cold pressing that step 1 is obtained, slitting, welding, with to electrode, be isolated Film assembles to obtain naked battery core, enters shell/enter bag later, drying, fluid injection, chemical conversion, shaping obtain finished product electrochemical cell;
Applying external force is the magnetic field for applying the angle between magnetic induction line and collector and being greater than or equal to 45 °, and application time is slurry Before drying.
2. a kind of electrochemical cell described in claim 1, it is characterised in that: the buffer layer with a thickness of the μ of 0.336nm~2 m;The ratio that the quality of the bonding agent accounts for the quality of the buffer layer is 0.5%~10%, and the quality of the conductive agent accounts for institute The ratio for stating the quality of buffer layer is 90%~99.5%.
3. a kind of electrochemical cell described in claim 1, it is characterised in that: the bonding agent be Kynoar (PVDF), At least one of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR);The conductive agent further includes that conductive black, carbon are received At least one of mitron, conductive carbon fibre;The ratio that the quality of the graphene accounts for the gross mass of the conductive agent is 10% ~100%.
4. a kind of electrochemical cell described in claim 1, it is characterised in that: the graphene is graphene oxide.
5. a kind of electrochemical cell described in claim 1, it is characterised in that: the graphene is unmodified graphene.
6. a kind of electrochemical cell described in claim 1, it is characterised in that: the graphene is modified graphene.
7. a kind of electrochemical cell described in claim 1, it is characterised in that: the quality of the graphene of angle theta≤30 ° accounts for graphite The ratio that the quality that the ratio of alkene total amount is greater than or equal to the graphene of 50% or/and angle theta≤45 ° accounts for graphene total amount is big In or equal to 70%.
8. a kind of electrochemical cell described in claim 1, it is characterised in that: the electrochemical cell includes nickel-metal hydride battery, nickel Cadmium cell, lead-acid battery, lithium ion battery, capacitor, Zinc ion battery, lithium-sulfur cell or sodium-ion battery.
9. electrochemical cell described in a kind of claim 1, which is characterized in that the solid content of slurry described in step 1 is less than or waits In 6%;The drying is freeze-drying or heat drying.
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CN106784996A (en) * 2017-01-16 2017-05-31 安徽益佳通电池有限公司 A kind of high power density lithium ion battery
CN108288714B (en) * 2018-01-27 2019-01-29 深圳名飞远科技有限公司 A kind of modified copper foil electrode of graphene for silicon-based anode power battery
CN109037585A (en) * 2018-08-03 2018-12-18 江苏芯界新能源科技有限公司 The preparation method of negative electrode of lithium ion battery substrate
CN111490253A (en) * 2019-01-29 2020-08-04 宁德时代新能源科技股份有限公司 Negative pole piece and lithium ion secondary battery thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103380519A (en) * 2011-02-18 2013-10-30 丰田自动车株式会社 Lithium-ion secondary cell and method for manufacturing same
CN103430360A (en) * 2011-03-11 2013-12-04 丰田自动车株式会社 Non-aqueous electrolyte secondary battery and manufacturing method thereof
CN104201358A (en) * 2014-09-26 2014-12-10 南京中储新能源有限公司 Carbon-sulfur composite positive electrode wrapped by nano-polyaniline and preparation method of carbon-sulfur composite positive electrode

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004220926A (en) * 2003-01-15 2004-08-05 Matsushita Electric Ind Co Ltd Negative electrode for nonaqueous electrolyte secondary battery
CN102208598B (en) * 2011-05-12 2014-03-12 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof
US9553299B2 (en) * 2011-07-29 2017-01-24 Toyota Jidosha Kabushiki Kaisha Lithium-ion secondary battery
TWI533497B (en) * 2013-08-28 2016-05-11 Current collection layer structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103380519A (en) * 2011-02-18 2013-10-30 丰田自动车株式会社 Lithium-ion secondary cell and method for manufacturing same
CN103430360A (en) * 2011-03-11 2013-12-04 丰田自动车株式会社 Non-aqueous electrolyte secondary battery and manufacturing method thereof
CN104201358A (en) * 2014-09-26 2014-12-10 南京中储新能源有限公司 Carbon-sulfur composite positive electrode wrapped by nano-polyaniline and preparation method of carbon-sulfur composite positive electrode

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