CN102593464B - Current collector and preparation method thereof - Google Patents
Current collector and preparation method thereof Download PDFInfo
- Publication number
- CN102593464B CN102593464B CN201210050410.8A CN201210050410A CN102593464B CN 102593464 B CN102593464 B CN 102593464B CN 201210050410 A CN201210050410 A CN 201210050410A CN 102593464 B CN102593464 B CN 102593464B
- Authority
- CN
- China
- Prior art keywords
- graphene
- current collector
- coating
- slurry
- collector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 79
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000005030 aluminium foil Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000523 sample Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 abstract description 25
- 239000011888 foil Substances 0.000 abstract description 23
- 239000011149 active material Substances 0.000 abstract description 21
- 239000010410 layer Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- -1 Kynoar Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a current collector and a preparation method thereof. The current collector comprises a current collector foil and at least one surface of the current collector foil is coated with coating layers containing graphene and a binder. The preparation method comprises the following steps of dispersing graphene and the binder in a solvent to obtain slurry, coating the slurry on at least one surface of the current collector foil and drying. Graphene of the coating layer has a two-dimensional sheet structure and thus the graphene forms a uniform and compact coating on the surface of the current collector foil so that a contact area of the graphene and the surface of the current collector is greatly improved; a conductive contact between an active material and the current collector is improved; the interface resistance of the current collector and the active material is effectively reduced; and internal resistance of a cell is reduced. Contact areas of graphene layers paved on the surface of the current collector and contact areas of the graphene layers and the current collector are large and thus interactional forces are strong; falling off is difficult; adhesive forces are strong; separation of the active material and the current collector is avoided in charging and discharging; and internal resistance reduction is promoted.
Description
Technical field
The present invention relates to lithium secondary battery field, relate in particular to a kind of collector and preparation method thereof.
Background technology
Lithium secondary battery, as a kind of high power capacity, long-life energy-storage system, has obtained being widely used in small portable electronic product, and its application prospect in high power electrokinetic cell and large capacity energy-storage battery has more attracted global sight.The research and development of high performance lithium ion battery are vital tasks in electrochemical energy storage field.
In lithium secondary battery, active material is evenly coated aluminium foil or Copper Foil collection liquid surface, and collector is collected and exported to external circuit by electronics electrochemical reaction being produced with the physical contact of active material, thereby realizes chemical energy and be converted into the process of electric energy.Can know by inference thus, contacting between collector and active material is the important factor in order of lithium ion battery charge-discharge performance.
In conventional lithium secondary battery pole piece manufacture craft, active material slurry is directly coated aluminium foil or copper foil surface at present, realizes active material be fixed on collection liquid surface after being dried by binding agent.But, there is the defect of following two aspects in such structural design: 1) contact area between metal collector and the active material particle of rigidity is limited, interface resistance is larger, cause the rising of the internal resistance of cell, for battery performance particularly the performance under high current charge-discharge condition there is negative effect; 2) adhesion strength of binding agent is limited, and in lasting charge and discharge process, the expansion that is easy to occur between active material and collector departs from, and causes the internal resistance of cell further to strengthen, and the security performance of cycle life and battery is affected.Therefore, reduce the interface resistance between collector and active material, the adhesion strength improving is between the two the important means that promotes lithium secondary battery performance.
It is the main path that realizes above-mentioned target that collector is carried out to surface treatment.The method of having reported at present mainly contains two kinds, and a kind of is, by the method for chemistry or physics, collector is carried out to surface etch, forms concavo-convex not clear rough surface, thereby improves the contact area of collector and active material, and strengthens adhesive force.But the method technical matters is had relatively high expectations, cost is comparatively expensive, is unfavorable for large-scale need of production.Another kind method is to apply the thin layer containing electric conducting material at collection liquid surface, this thin layer need to have good conductive capability, higher specific area, good adhesive property, and there is better deformability with respect to metal collector, thereby increase the conductive contact between active material and collector, reduce interface resistance, and improve adhesion strength between the two.The method can be utilized existing cell coating equipment simultaneously, easy and simple to handle, with low cost, is an important development direction of collection liquid surface modification.
In above-mentioned conductive coating, the selection of electric conducting material is undoubtedly most important link.Consider the selection that material with carbon element is best suited for from electric conductivity and cost.Material with carbon element is of a great variety, common are graphite, carbon black, carbon nano-tube and carbon fiber etc.But because graphite or carbon black are three-dimensional structures, graphite or carbon black form some contact with contacting of Copper Foil, thereby make the conductive coating that forms not fine and close, easily come off, affect to a certain extent interface resistance and adhesion strength, finally affect the performance of battery.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of secondary cell collector, coating modified by collection liquid surface being carried out to Graphene, reduce the contact resistance between collector and active material, improved cohesive force between the two, finally realized the General Promotion to battery performance.
The invention discloses a kind of collector, comprise collector foil, described collector foil at least has the coating of graphene-containing and binding agent in one side.
The preparation method who the invention also discloses a kind of collector, comprising:
Graphene and binding agent are disperseed in solvent, form slurry; Described slurry coating is upper at least one surface of collector foil, form the coating that contains Graphene and binding agent; Then be dried.
Preferably, the mass ratio of described Graphene and binding agent is (1～49): 1.
Preferably, the number of plies of described Graphene is individual layer or between 1～30 layer; The carbon content > 95wt% of described Graphene, the body conductance > 100S/cm of described Graphene.
Preferably, the method for described dispersion be stirring, high speed shear, emulsification and ultrasonic in one or more.
Preferably, described solvent is mixed solvent or the 1-METHYLPYRROLIDONE of water, water and ethanol.
Preferably, after the described step that Graphene and binding agent are disperseed in solvent, also comprise: deaeration is processed and sieved.
Preferably, the solid content of described slurry is 0.2～20wt%, and the viscosity of described slurry is 50～5000mPas.
Preferably, the thickness of described coating is 0.005～10 micron.
Preferably, described coating is 30%～100% in the coverage rate on collector foil surface.
Preferably, described coating also comprises one or more in graphite, carbon black, acetylene black, carbon nano-tube, carbon fiber.
The invention provides a kind of preparation method of collector, compared with prior art, the collection liquid surface of preparing according to method provided by the invention has the coating of graphene-containing and binding agent.In coating, graphene conductive performance is very excellent, and its conductivity can reach 10
6s/cm, can strengthen the conductivity between collector and active material, reduces the internal resistance of battery; Simultaneously because the exclusive two dimension of Graphene is laminar structured, make Graphene form even, fine and close coating on collector foil surface, greatly improve the contact area of Graphene on collector foil surface, increase the conductive contact between active material and collector, can effectively reduce the interface resistance between collector and active material, reduce internal resistance; Be laid between the graphene sheet layer of collection liquid surface and and collector foil between contact area large, interaction force is strong, difficult drop-off, adhesion strength is strong, in the process discharging and recharging, can there is not the disengaging between active material and collector, be conducive to reduce internal resistance, thereby improve the performance of battery comprehensively.
Brief description of the drawings
Fig. 1 is the structural representation of the collector prepared of the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the collector prepared of the embodiment of the present invention 1;
Fig. 3 is the AC impedance spectrogram before and after the test of battery high magnification;
Fig. 4 is the internal resistance variation diagram of battery in different phase;
Fig. 5 is the discharge curve of battery under 5C multiplying power;
Fig. 6 is battery battery surface temperature variations while discharging under 5C multiplying power;
Fig. 7 is the discharge curve of battery in the time of-20 DEG C.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of secondary cell collector, comprise collector foil, described collector foil at least has the coating of graphene-containing and binding agent in one side.Described collector foil is preferably Copper Foil or aluminium foil.
As preferred version, in described coating, the content of Graphene is 50wt%～98wt%.The effect of binding agent in coating be make Graphene can firm attachment on collector, be unlikely in use to come off.Binding agent is originally as insulator, and addition can affect the conductivity of Graphene coating.Therefore, the addition of binding agent is preferably 2wt%～50wt%, too much can cause collector too high in resistance, and I haven't seen you for ages excessively affects the adhesion strength of Graphene coating.Described binding agent is preferably one or more in sodium carboxymethylcellulose, Kynoar, polytetrafluoroethylene, butadiene-styrene rubber and LA series binding agent.
The present invention also provides a kind of preparation method of secondary cell collector, comprising: Graphene and binding agent are disperseed in solvent, form slurry; Described slurry coating is upper at least one surface of collector foil, form the coating that contains Graphene and binding agent; Then be dried.
In order to make coating have good conductivity, as preferred version, the mass ratio of above-mentioned Graphene and binding agent is (1～49): 1; The number of plies of described Graphene is preferably between individual layer or 1～30 layer, in layer, is sp
2carbon atom six sides of hydridization are tightly packed, the coating carbon material that interlayer closes with π bond; The carbon content > 95wt% of Graphene, bulk conductivity > 100S/cm.Described binding agent is preferably one or more in sodium carboxymethylcellulose, Kynoar, polytetrafluoroethylene, butadiene-styrene rubber and LA series binding agent.
In the preparation method of collector, the method for above-mentioned dispersion is preferably stirring, high speed shear, emulsification, one or more in ultrasonic.In order to make in coating Graphene and binding agent more tiny evenly, as preferred version, after the above-mentioned step that Graphene and binding agent are disperseed in solvent, also comprise: deaeration is processed and sieved, thereby ensures to form the coating of even compact on collector foil.According to the present invention, above-mentioned slurry can apply by coating process, and described coating process is preferably coating machine coating, casting, dip coating or printing.Described coating can preferably adopt continuous or discrete application pattern.Above-mentioned dry temperature is preferably 30～200 DEG C.As preferred version, described dry immediately coating process synchronously carries out, also can be dry in the lump after coating finishes.
In preparation method, described solvent is preferably mixed solvent or the nitrogen methyl pyrrolidone of water, water and ethanol, in described water and alcohol mixed solvent, the mass ratio of water and ethanol is preferably (20～400): 1, and more preferably (50～300): 1.The solid content of described slurry is preferably 0.2～20wt%, the viscosity of described slurry is preferably 50～5000mPas, more preferably 500～1000mPas, the viscosity Tai little Huo Tai big city of slurry affects coating or the printing performance of slurry, uniformity and the continuity of coating are affected, even cannot be coated with or print.In order to make coating have better conductivity, the present invention also can add other electric conducting materials in solvent, is preferably one or more in graphite, carbon black, acetylene black, carbon nano-tube, carbon fiber.
According to the present invention, coating, as the non-active material in electrode, itself is not contributed for the capacity of battery, can reduce along with the increase of coating layer thickness on the contrary the energy density of battery, and therefore, in theory, coating is to get over Bao Yuehao.But along with coating attenuate, likely its performance is had to adverse effect.For conventional material with carbon element, the scope of conductive coating is conventionally at one micron to tens microns.And for Graphene, due to the distinguished two-dimensional structure of Graphene, even if its thickness only has tens to hundreds of nanometer, can both play good effect, the thickness of coating of the present invention is preferably 0.005～10 micron, more preferably 0.1～5 micron.Coating is preferably 30%～100% in the coverage rate on collector foil surface.
The present invention has prepared secondary cell collector, at least one mask of the collector foil of preparation has the coating of graphene-containing and binding agent, due to the electric conductivity excellence of Graphene, greatly strengthen the conductivity between collector and active material, the exclusive two-dimensional structure of Graphene simultaneously, make Graphene can form the coating of even compact on collector foil surface, increase the conductive contact between collector and active material, reduce interface resistance, and be laid between the graphene sheet layer on collector foil surface and and collector foil between contact area large, interaction force is strong, difficult drop-off, adhesion strength is strong.Therefore can effectively improve the performance of battery by there is the coating of Graphene in the coating of collector foil surface.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of collector provided by the invention is described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Taking 2g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, graphene-containing 8g in Graphene slurry, add 2000g deionized water to regulate slurry viscosity, viscosity control is 800mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 500 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 4.553E
-6ohm.cm.
Fig. 1 is the structural representation of the collector prepared of embodiment 1, and this schematic diagram comprises tinsel 1, and is overlying on the coating 2 on described tinsel 1 surface, and coating comprises Graphene and binding agent.
Collection liquid surface prepared by the present embodiment scans, and Fig. 2 is the scanning electron microscope (SEM) photograph of graphene conductive coating, as can be seen from the figure, and the densification that is evenly distributed on collector foil of graphene conductive coating.
Embodiment 2
Taking 1.5g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 30g Graphene slurry and 0.5g conductive carbon black (Super P) to be uniformly mixed, in Graphene slurry, contain 8g Graphene, add 2000g deionized water to regulate slurry viscosity, viscosity control is 600mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 200 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 4.761E
-6ohm.cm.
Embodiment 3
Take 8g graphene powder and join in 500g nitrogen methyl pyrrolidone and soak 8 hours, ultrasonic dispersion 10 minutes, supersonic frequency is 15KHz; Taking 2g Kynoar joins in 1000g nitrogen methyl pyrrolidone, employing mixer mixes, and then after adding the ultrasonic dispersion of 508g, Graphene slurry is uniformly mixed, then add 1500g nitrogen methyl pyrrolidone to regulate slurry viscosity, viscosity control is 1000mPas, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 200 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.25N, and adopting the resistivity of four probe method test pole piece is 5.653E
-6ohm.cm.
Embodiment 4
Take 8g graphene powder and join in 500g nitrogen methyl pyrrolidone and soak 8 hours, then ultrasonic dispersion 10 minutes, supersonic frequency is 15KHz; Taking 1.5g Kynoar adds in 1000g nitrogen methyl pyrrolidone, employing mixer mixes, add 0.5g SP to be uniformly mixed, and then add the 508g Graphene slurry after ultrasonic dispersion to be uniformly mixed, add 1500g nitrogen methyl pyrrolidone to regulate slurry viscosity, viscosity control is 1000mPas, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 500 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.25N, and adopting the resistivity of four probe method test pole piece is 5.362E
-6ohm.cm.
Embodiment 5
Taking 53.3g LA133 (solid content is 15%) joins in 1100g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, in Graphene slurry, contain 8g Graphene, add 1900g deionized water to regulate slurry viscosity, viscosity control is 800mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 100 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.6N, and adopting the resistivity of four probe method test pole piece is 4.453E
-6ohm.cm.
Embodiment 6
Taking 2g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, in Graphene slurry, contain 8g Graphene, add 2000g deionized water to regulate slurry viscosity, viscosity control is 800mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to copper foil surface uniformly by transfer type coating machine, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 200 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 1.353E
-6ohm.cm.
Embodiment 7
Taking 2g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, in Graphene slurry, contain the Graphene of 8g, add 2000g deionized water to regulate slurry viscosity, viscosity control is 200mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by screen process press, and dries in air dry oven, obtaining one side coating layer thickness is 200 nanometers, and is the graphene conductive coating of discontinuous gridding, and Graphene coating is 50% in the coverage rate of aluminium foil surface.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 3.632E
-6ohm.cm.
Embodiment 8
Taking 2g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, in Graphene slurry, contain 8g Graphene, add 2000g deionized water to regulate slurry viscosity, viscosity control is 200mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by extrusion coater, and dries in air dry oven, obtaining one side coating layer thickness is the graphene conductive coating of 100 nanometers.
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 4.372E
-6ohm.cm.
Comparative example 1
Adopt the tinsel of buying from the market as collector, tinsel is aluminium foil.
Adopt the collector of embodiment 1 to prepare 18650 column type power lithium-ion batteries, be numbered: battery 1; Adopt the collector of comparative example 1 to prepare lithium ion battery simultaneously, be numbered: battery 2.Test the ac impedance spectroscopy of above-mentioned two kinds of battery high magnifications front and back, test result as shown in Figure 3, Fig. 3 is the AC impedance spectrogram before and after battery 1 and battery 2 high magnification tests, in Fig. 3, ■ curve is the AC impedance spectral curve before battery 2 high magnification tests, ● curve is the AC impedance spectral curve after battery 2 high magnification tests, ▲ curve is the AC impedance spectral curve before battery 1 high magnification test, ★ curve is the AC impedance spectral curve after battery 1 high magnification test, as can be seen from Figure 3, the internal resistance of battery 1 will be lower than the internal resistance of battery 2.
The internal resistance of battery 1 and battery 2 is tested, test result as shown in Figure 4, Fig. 4 is battery 1 and the battery 2 internal resistance variation diagram in different phase, in Fig. 4, ■ curve is the internal resistance change curve of battery 2, ▲ curve is the internal resistance change curve of battery 1, as can be seen from Figure 4, the internal resistance of battery 1 reduces by 10%～50% compared with the internal resistance of battery 2, and the internal resistance of battery 1 changes more steady.
Voltage when battery 1 and battery 2 are discharged under 5C multiplying power is tested, test result as shown in Figure 5, Fig. 5 is battery 1 and the discharge curve of battery 2 under 5C multiplying power, curve a is the discharge curve of battery 1 under 5C multiplying power, curve b is the discharge curve of battery 2 under 5C multiplying power, as can be seen from Figure 5, battery 1 is pressed in the electric discharge under 5C multiplying power and is improved 0.1～0.2V than battery 2.
The surface temperature that battery 1 and battery 2 are discharged under 5C multiplying power changes tests, test result as shown in Figure 6, Fig. 6 is battery 1 and battery 2 battery surface variations in temperature while discharging under 5C multiplying power, in Fig. 6, curve a is the surface temperature change curve that battery 2 discharges under 5C multiplying power, curve b is the surface temperature change curve that battery 1 discharges under 5C multiplying power, as can be seen from Figure 6, surface temperature when battery 1 discharges under 5C multiplying power completely than battery 2 reduces more than 20 DEG C.
By battery 1 and battery 2, discharge capacity at-20 DEG C is tested, test result as shown in Figure 7, Fig. 7 is battery 1 and the discharge curve of battery 2 in the time of-20 DEG C, and in Fig. 7, curve a is the discharge curve of battery 1 in the time of-20 DEG C, and curve b is the discharge curve of battery 2 in the time of-20 DEG C.As can be seen from Figure 7, battery 1 promotes more than 20% than battery 2 discharge capacity at-20 DEG C.
From above test result, adopt in battery use procedure prepared by collector of the present invention, for the battery that adopts conventional collector to prepare, internal resistance stability is better, reduce internal resistance, strengthened cyclical stability, the performance of battery is improved.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (1)
1. a preparation method for collector, is characterized in that, comprising:
Taking 2g sodium carboxymethylcellulose joins in 1000g deionized water, employing mixer mixes, and then add 40g Graphene slurry to be uniformly mixed, in Graphene slurry, contain the Graphene of 8g, add 2000g deionized water to regulate slurry viscosity, viscosity control is 200mPas, finally adds 30g ethanol to carry out low speed vacuum and stirs deaeration processing, crosses 150 eye mesh screens and obtains slurry; This slurry is coated on to aluminium foil surface uniformly by screen process press, and dries in air dry oven, obtaining one side coating layer thickness is 200 nanometers, and is the graphene conductive coating of discontinuous gridding, and Graphene coating is 50% in the coverage rate of aluminium foil surface;
Adopting peeling strength test machine to record peel strength above-mentioned prepared collector is 0.5N, and adopting the resistivity of four probe method test pole piece is 3.632E
-6ohm.cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050410.8A CN102593464B (en) | 2012-02-29 | 2012-02-29 | Current collector and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050410.8A CN102593464B (en) | 2012-02-29 | 2012-02-29 | Current collector and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102593464A CN102593464A (en) | 2012-07-18 |
| CN102593464B true CN102593464B (en) | 2014-11-05 |
Family
ID=46481826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210050410.8A Active CN102593464B (en) | 2012-02-29 | 2012-02-29 | Current collector and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102593464B (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000939B (en) * | 2012-12-12 | 2015-06-03 | 湖南立方新能源科技有限责任公司 | Lithium ion battery with graphene composite membrane as current collector and preparation method thereof |
| CN103022505B (en) * | 2012-12-12 | 2016-01-20 | 湖南立方新能源科技有限责任公司 | Lithium ion battery being collector body with Graphene dialysis membrane and preparation method thereof |
| CN103903876B (en) * | 2012-12-26 | 2016-06-22 | 海洋王照明科技股份有限公司 | A kind of preparation method of flexible current-collecting body |
| CN103311502A (en) * | 2013-05-08 | 2013-09-18 | 上海新池能源科技有限公司 | Metal foil/graphene composite electrode plate and preparation method thereof |
| CN103413693B (en) * | 2013-05-24 | 2016-01-13 | 宁波南车新能源科技有限公司 | A kind of manufacture method of ultracapacitor |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN103500812B (en) * | 2013-09-16 | 2016-04-06 | 杨海燕 | A kind of doped graphene prepares the method for high-conductivity slurry |
| CN104600320A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Functional copper foil based on graphene and preparation method thereof |
| CN104916809B (en) * | 2014-03-12 | 2017-06-09 | 中国科学院金属研究所 | A kind of integrated flexible electrode |
| CN104752682B (en) * | 2015-03-16 | 2017-11-14 | 山东玉皇新能源科技有限公司 | A kind of sulphur of lithium-sulfur cell/carbon composite anode material preparation method |
| CN104752725A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Cathode material for high-capacity graphene lithium sulphur battery and preparation method of cathode material |
| CN105024082A (en) * | 2015-06-19 | 2015-11-04 | 东莞市翔丰华电池材料有限公司 | Water-based conductive ink for lithium ion battery and preparation method thereof |
| CN106362929A (en) * | 2015-07-20 | 2017-02-01 | 北京中科云腾科技有限公司 | Grapheme-copper foil composite heat-conduction film and preparation method for same |
| CN106374111B (en) * | 2015-07-20 | 2019-09-17 | 北京中科云腾科技有限公司 | A kind of graphene composite metal membrane and preparation method thereof |
| CN105140542A (en) * | 2015-08-28 | 2015-12-09 | 张家港讴德电池技术有限公司 | Grid lowering interface resistance and preparation method thereof |
| CN105449223A (en) * | 2015-11-18 | 2016-03-30 | 青岛领军节能与新材料研究院 | Manufacturing method for high-safety and high-capacity lithium ion battery |
| CN105932208A (en) * | 2016-04-15 | 2016-09-07 | 合肥国轩高科动力能源有限公司 | Lithium ion battery ceramic diaphragm coated by binder LA133 and preparation method thereof |
| CN105826569A (en) * | 2016-05-24 | 2016-08-03 | 深圳市国创新能源研究院 | Lithium battery current collector and preparing method thereof |
| CN105932297B (en) * | 2016-06-12 | 2018-10-09 | 华南理工大学 | A kind of carbon nanotube conducting coating collector and its preparation process |
| EP3352187B1 (en) | 2016-06-17 | 2020-12-30 | TPR Co., Ltd. | Electric double layer capacitor |
| CN106784853B (en) * | 2016-09-27 | 2020-05-08 | 彭成信 | Graphene coated aluminum foil current collector and preparation method thereof |
| CN106252666A (en) * | 2016-10-11 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium ion battery negative collector |
| CN106328953A (en) * | 2016-10-12 | 2017-01-11 | 漳州万利达能源科技有限公司 | Current collector and preparation method thereof |
| CN106590375A (en) * | 2016-12-19 | 2017-04-26 | 镇江创智特种合金科技发展有限公司 | Aluminum-based graphene composite material |
| CN106848324B (en) * | 2017-01-06 | 2020-08-25 | 深圳市德方纳米科技股份有限公司 | Oily undercoat current collector for lithium ion battery and preparation method and application thereof |
| CN107546391B (en) * | 2017-07-14 | 2020-10-27 | 中国第一汽车股份有限公司 | Polydopamine and graphene composite coating |
| CN107681160A (en) * | 2017-09-21 | 2018-02-09 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of utter misery aluminium foil |
| CN109841424B (en) * | 2017-11-28 | 2021-03-02 | 东莞东阳光科研发有限公司 | Carbon-coated current collector foil containing spider silk fibers and preparation method and application thereof |
| CN109950473A (en) * | 2019-03-29 | 2019-06-28 | 柯良节 | A kind of lithium-sulphur cell positive electrode and preparation method thereof |
| CN111180741A (en) * | 2020-01-03 | 2020-05-19 | 松山湖材料实验室 | Carbon-coated current collector coated with three-dimensional graphene powder and preparation method thereof |
| CN112151806A (en) * | 2020-09-15 | 2020-12-29 | 浙江长宇新材料有限公司 | Ultra-light multilayer composite current collector and preparation method thereof |
| CN114243026B (en) * | 2021-11-17 | 2023-09-05 | 荣烯新材(北京)科技有限公司 | Preparation method and equipment of graphene current collector |
| CN116964768A (en) | 2022-01-28 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Surface treatment composition, electrode, method for producing same, secondary battery, and device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201450056U (en) * | 2009-07-01 | 2010-05-05 | 江苏双登集团有限公司 | Polyester lithium ion electrokinetic cell pole piece |
| CN102208598A (en) * | 2011-05-12 | 2011-10-05 | 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI467840B (en) * | 2005-09-02 | 2015-01-01 | A123 Systems Inc | Nanocomposite electrodes and related devices |
| US9356281B2 (en) * | 2008-05-20 | 2016-05-31 | GM Global Technology Operations LLC | Intercalation electrode based on ordered graphene planes |
-
2012
- 2012-02-29 CN CN201210050410.8A patent/CN102593464B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201450056U (en) * | 2009-07-01 | 2010-05-05 | 江苏双登集团有限公司 | Polyester lithium ion electrokinetic cell pole piece |
| CN102208598A (en) * | 2011-05-12 | 2011-10-05 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102593464A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102593464B (en) | Current collector and preparation method thereof | |
| Su et al. | Enhancement of the Cyclability of a Si/Graphite@ Graphene composite as anode for Lithium-ion batteries | |
| CN107978732B (en) | Pole piece and battery | |
| CN107068972A (en) | The ternary material anode pole piece and its lithium ion battery of a kind of quick charge | |
| CN102544502A (en) | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery | |
| CN112599928A (en) | Composite diaphragm with lithium supplementing effect, preparation method thereof and lithium ion battery | |
| CN105261760A (en) | Lithium ion battery waterborne positive electrode composite collector, positive plate, manufacturing methods for lithium ion battery waterborne positive electrode composite collector and positive plate, and lithium ion battery | |
| Sun et al. | Effect of poly (acrylic acid)/poly (vinyl alcohol) blending binder on electrochemical performance for lithium iron phosphate cathodes | |
| CN106654179A (en) | Composite conductive agent preparation method, lithium battery positive plate preparation method and lithium battery preparation method | |
| CN109817953A (en) | Prelithiation silicon-carbon cathode material and preparation method thereof and lithium ion battery | |
| CN107958993A (en) | A kind of based lithium-ion battery positive plate of combined conductive agent layering cladding and preparation method thereof | |
| CN109037592A (en) | Lithium ion battery positive plate, preparation method thereof and lithium ion battery | |
| CN108899522B (en) | High-capacity silicon-carbon negative electrode material, preparation method and application | |
| CN103928657A (en) | High-power lithium ion battery pole piece and preparation process thereof | |
| CN111613769A (en) | Positive electrode and preparation method and application thereof | |
| CN102969509A (en) | Preparation method of lithium ion battery silicon carbon composite material | |
| CN103137942B (en) | The preparation method of a kind of ferric phosphate lithium cell collector and positive plate | |
| CN106356536A (en) | Lithium ion battery negative electrode and preparation method thereof | |
| Liu et al. | Blended spherical lithium iron phosphate cathodes for high energy density lithium–ion batteries | |
| CN109950549A (en) | A kind of lithium ion battery collector and preparation method thereof | |
| CN108878893A (en) | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof | |
| CN105977495B (en) | A kind of preparation method of affluxion body in lithium ion batteries graphite paper | |
| CN104882631A (en) | Method for improving uniform heat dispersion performance of lithium ion battery electrode piece | |
| CN105826569A (en) | Lithium battery current collector and preparing method thereof | |
| CN210379259U (en) | Positive plate for improving rate capability of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240506 Address after: 315201 No. 1818, Zhong Guan Xi Road, Zhuang City Street, Zhenhai District, Ningbo, Zhejiang. Patentee after: NINGBO GRAPHENE INNOVATION CENTER Co.,Ltd. Country or region after: China Address before: No. 519 Zhuangshi Avenue, Haiqu District, Ningbo City, Zhejiang Province, 315201 Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Country or region before: China |