CN105449221B - The preparation method of collector - Google Patents

The preparation method of collector Download PDF

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Publication number
CN105449221B
CN105449221B CN201410269132.4A CN201410269132A CN105449221B CN 105449221 B CN105449221 B CN 105449221B CN 201410269132 A CN201410269132 A CN 201410269132A CN 105449221 B CN105449221 B CN 105449221B
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Prior art keywords
carbon nanotube
layer
nanotube layer
metal layer
collector
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CN105449221A (en
Inventor
魏洋
吴扬
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Priority to CN201410269132.4A priority Critical patent/CN105449221B/en
Priority to TW103123449A priority patent/TWI508360B/en
Priority to US14/738,955 priority patent/US20150361573A1/en
Publication of CN105449221A publication Critical patent/CN105449221A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54Electroplating of non-metallic surfaces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils

Abstract

The present invention relates to a kind of preparation method of collector, including:A carbon nanotube layer is provided, the carbon nanotube layer includes multiple micropores and relative first surface and second surface;A first metal layer is electroplated in the first surface of the carbon nanotube layer;A second metal layer is electroplated in the second surface of the carbon nanotube layer, forms a CNT composite bed;And tear the CNT composite bed, the carbon nanotube layer is set to be divided into the first sub- carbon nanotube layer and the second sub- carbon nanotube layer, the first sub- carbon nanotube layer is attached at the surface of the first metal layer, and the second sub- carbon nanotube layer is attached at the surface of the second metal layer.

Description

The preparation method of collector
Technical field
The present invention relates to a kind of preparation method of collector, more particularly to a kind of collector based on carbon nano tube structure Preparation method.
Background technology
Collector is an important chief component of electrochemical cell.In an electrochemical cell, collection liquid surface leads to Often carry electrode active material and contact electrolyte, electron channel can be provided for electrochemical reaction, to accelerate electronics transfer, and will Electric transmission forms electric current to external circuit.Therefore, the performance of collector and the performance of electrochemical cell are closely related.
Existing collector is generally prepared by conductive metal layer, such as copper foil and aluminium foil.However, these metal levels are easy to One layer of passivating film is oxidized to form, or is corroded to form an insulating barrier in the electrolytic solution, the passivating film or insulating barrier are very big Ground adds the contact resistance of electrode active material and the metal level, so as to reduce the capacity of electrochemical cell and energy conversion Efficiency.
The content of the invention
In view of this, it is necessory to provide a kind of collector with smaller contact resistance between electrode active material Preparation method.
A kind of preparation method of collector, including:A carbon nanotube layer is provided, the carbon nanotube layer has relative One surface and second surface, the carbon nanotube layer include multiple CNTs, at least part CNT be arranged at intervals to be formed it is more Individual micropore;A first metal layer is electroplated in the first surface of the carbon nanotube layer, in the second surface of the carbon nanotube layer A second metal layer is electroplated, forms a CNT composite bed;And the CNT composite bed is torn, make the CNT Layer is divided into the first sub- carbon nanotube layer and the second sub- carbon nanotube layer, and the first sub- carbon nanotube layer is attached at described first The surface of metal level, the second sub- carbon nanotube layer are attached at the surface of the second metal layer.
A kind of preparation method of collector, including:One the first metal layer is provided;A carbon nanotube layer is provided, the carbon is received Mitron layer includes relative first surface and second surface, and the first surface of the carbon nanotube layer is attached at into first gold medal Belong to the surface of layer;A second metal layer is electroplated in the second surface of the carbon nanotube layer, forms a CNT composite bed;And The CNT composite bed is torn, the carbon nanotube layer is formed one first sub- carbon nanotube layer and is attached at first gold medal Belong to the surface of layer, one second sub- CNT is attached at the surface of the second metal layer layer by layer, forms two collectors.
Compared with prior art, the preparation method of collector provided by the present invention, made by way of plating described CNT is firmly held between the first metal layer and second metal layer, and the mode then separated again forms collector, can More than two collectors are once obtained, the carbon nanotube layer is firmly fixed and the first metal layer or the second metal Layer surface, and blocked metal level directly to be contacted with electrolyte, so as to prevent the corrosion between electrolyte and metal level anti- Should, reduce influence of the corrosion product to the contact resistance between collector and electrode material layer, the battery capacity of raising and turn Change efficiency.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method for the collector that first embodiment of the invention provides.
Fig. 2 is the structural representation of carbon nano-tube film in the collector that first embodiment of the invention provides.
Fig. 3 is the structural representation of carbon nanotube layer in the collector that first embodiment of the invention provides.
Fig. 4 is flow chart of the first embodiment of the invention in the carbon nanotube layer electroplating surface metal layer.
Fig. 5 is to tear the CNT composite bed in the preparation method for the collector that first embodiment of the invention provides Flow chart.
Fig. 6 is the flow chart of the preparation method for the collector that second embodiment of the invention provides.
Main element symbol description
Collector 10
Carbon nanotube layer 110
The first metal layer 120
Second metal layer 130
First surface 111
Micropore 112
Second surface 113
CNT composite bed 11
First sub- carbon nanotube layer 114
Second sub- carbon nanotube layer 116
Electrode slice 140
Specific examples below will combine above-mentioned accompanying drawing and further illustrate the present invention.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments, collector provided by the invention and preparation method thereof is made further Describe in detail.
Referring to Fig. 1, the present invention also provides a kind of preparation method of collector 10, comprise the following steps:
Step S10, there is provided a carbon nanotube layer 110, the carbon nanotube layer 110 include relative first surface 111 and Second surface 113;
Step S11, a first metal layer 120 is electroplated in the first surface 111 of the carbon nanotube layer 110, in the carbon The second surface 113 of nanotube layer 110 electroplates a second metal layer 130, forms a CNT composite bed 11;And
Step S12, the CNT composite bed 11 is torn, the carbon nanotube layer 110 is divided into the first sub- carbon and receive 114 and second sub- carbon nanotube layer 116 of mitron layer, the first sub- carbon nanotube layer 114 are attached at the first metal layer 120 Surface, the second sub- carbon nanotube layer 116 is attached at the surface of the second metal layer 130.
In step slo, the carbon nanotube layer 110 may be disposed at a substrate(It is not shown)Surface, can also pass through one Fixed frame is vacantly set, so that the carbon nanotube layer 10 can vacantly be set in follow-up solution.The substrate can be Insulated substrate or electrically-conductive backing plate.Because the carbon nanotube layer 110 is a self supporting structure, therefore spaced branch can be passed through Support body is supported, and the carbon nanotube layer 110 is vacantly set.The carbon nano tube structure may include that the carbon of multilayer laminated setting is received Mitron film, the multilayer carbon nanotube film layer is folded and arranged in a crossed manner, between the CNT in different layers carbon nano-tube film mutually Interweave and form a network structure.Each carbon nano-tube film includes multiple CNTs, and the multiple CNT is in the same direction It is arranged of preferred orient.The preferred orientation refers to the basic court of overall bearing of trend of most of CNTs in carbon nano-tube film Same direction.Moreover, the overall bearing of trend of most of CNTs is basically parallel to the surface of carbon nano-tube film.Enter one Step, most CNTs are joined end to end by Van der Waals force in the carbon nano-tube film.The carbon nanotube layer 110 includes Multiple micropores 112, the multiple micropore 112 run through the carbon nanotube layer along perpendicular to the direction of the thickness of carbon nanotube layer 110 110.In the present embodiment, the carbon nanotube layer 110 is vacantly set by a fixed frame.
In step s 11, the first metal layer 120 is formed by way of plating in the carbon nanotube layer 110 First surface 111.Specifically, the electro-plating method of the first metal layer 120 comprises the following steps:
Step S111, there is provided the solution containing metal ion;
Step S112, the carbon nanotube layer 110 is immersed in the solution, the first table of the carbon nanotube layer 110 Face 111 and second surface 113 are exposed in solution, and and interval setting parallel with the electrode slice in solution;
Step S113, an electrical potential difference is formed between the carbon nanotube layer 110 and the electrode slice, makes metal ion also Originally it was metal and electroplated the first surface 111 and second surface 113 in the carbon nanotube layer 110, and formed first metal Layer 120 and second metal layer 130.
In step S111, the forming method of the solution containing metal ion is unlimited, can in the solution as long as ensureing Form metal ion.The concentration of the metal ion can be according to required the first metal layer 120 and the thickness of second metal layer 130 Degree etc., which is actually needed, to be selected.In the present embodiment, the solution formed by way of copper sulphate is dissolved in the water copper from Sub- solution.
In step S112, the carbon nanotube layer 110 is arranged at intervals with the electrode slice, and the spacing distance distance is It can be 0.5 centimetre ~ 3 centimetres, can also be selected according to being actually needed.The electrode slice includes inertia graphite electrode piece, platinum electricity Pole piece, stainless steel electrode piece and layered carbon nano tubular construction, its area are more than or equal to the area of carbon nano-tube film.The electrode Piece plays a part of electrode, if good conductivity, and can meet to require with inertia.The carbon nanotube layer 110 is suspended in In the metal ion solution, specifically, because the carbon nanotube layer 110 is vacantly set by fixed frame, therefore soaked When entering in metal ion solution, the carbon nanotube layer 110 between fixed frame is suspended in the solution.In the present embodiment, The electrode slice is copper sheet, and the area of the copper sheet is more than the area of the carbon nanotube layer 110.
In step S113, an electrical potential difference is formed between carbon nanotube layer 110 and electrode slice, and make electrode slice and power supply Positive pole phase continuous cropping anode, carbon nanotube layer 110 and power cathode phase continuous cropping negative electrode, metal ion is in the CNT as negative electrode Reduction reaction occurs on layer 110, forms metallic particles and is attached on the tube wall of the CNT.In addition, in the mistake of plating Cheng Zhong, the surface of CNT forms multiple dangling bonds in the carbon nanotube layer 110 so that the metallic particles passes through described The dangling bonds of CNT are combined closely with the CNT.Further, the metallic particles is in the carbon nanotube layer 110 Surface link each other, formed a continuous structure so that the first metal layer 120 and second metal layer 130 are one Continuous structure.In addition, part metals ion reduction is the CNT table that metallic particles is attached to the opening position of micropore 112 Face, and cause the first metal layer 120 mutually to merge to form integrative-structure in the opening position of micropore 112 with second metal layer 130.
The method for forming electrical potential difference between the anode and the cathode includes applying constant current, constant pressure between the anode and the cathode Or scanning potential etc..In the present embodiment, between positive electrode and negative electrode formed electrical potential difference method for apply constant pressure, anode with The voltage applied between negative electrode is 0.5 ~ 1.2 volt, and the time is 0.5 hour ~ 4 hours.
Further, in step S112, the first metal layer 120 and second metal layer 130 can also be formed step by step, specifically , also the second surface 113 of the carbon nanotube layer 110 first can be attached at a substrate(It is not shown), only make first surface 111 In metal ion solution, first the first metal layer 120 is formed in the plating of first surface 111;Then first will be electroplate with again The carbon nanotube layer 110 of metal level 120 inverts, and makes the second surface 113 of the carbon nanotube layer 110 molten exposed to metal ion In liquid, and it is oppositely arranged with the electrode slice, then electroplates the second metal layer 130 in second surface 113.
Further, during second metal layer 130 is electroplated, part second metal layer 130 runs through the micropore 112, So as to be contacted with the first metal layer 120 and form integrative-structure, the carbon nanotube layer 110 is held on first gold medal Belong between layer 120 and second metal layer 130.It is appreciated that because the carbon nanotube layer 110 immerses the metal ion solution In, therefore, the metal ion is electroplated in the first surface 111 and second surface 113 of the carbon nanotube layer 110 simultaneously, i.e., The second metal layer 130 can be formed simultaneously with the first metal layer 120.
Further, plating is formed after the second metal layer 130, and it is clear using cleaning solution to can further include one The step of washing and drying the carbon nanotube layer 110, the first metal layer 120 and second metal layer 130, to remove residual Other impurities, and the first metal layer 120 and second metal layer 130 is more firmly bonded to the carbon nanotube layer 110 Surface.
In step s 12, the CNT composite bed 11 can by the CNT composite bed 11 it is relative two Individual surface applies the active force of opposite direction, the CNT composite bed 11 is divided for two parts.Please refer to fig. 5, institute The disconnection method for stating CNT composite bed 11 comprises the following steps:
Step S121, two surfaces relative to the CNT composite bed 11 apply the directed force F of opposite direction, F’;
Step S122, it is continuously applied the institute firmly F, F ', make the carbon nanotube layer 110 in the CNT composite bed 11 Separated from centre, be attached at the surface of the first metal layer 120 and second metal layer 130 respectively, form two collectors 10.
In step S121, described two directed force Fs, F ' big I are according to the carbon nanotube layer 110, first gold medal Category layer 120 and the thickness of second metal layer 130 are selected, so that the carbon nanotube layer 110 can separate.Described two works Firmly F, F ' put on two relative surfaces of CNT composite bed 11, so as to by CNT composite bed 11 along thickness side To separating, i.e., carbon nanotube layer 110 is divided into the first essentially identical sub- 114 and second sub- carbon of carbon nanotube layer of two panels area Nanotube layer 116, the surface for being attached at the first metal layer 120 and second metal layer 130 is corresponded to respectively, so as to form two The essentially identical collector 10 of area, and the area of the collector 10 is substantially equal to the CNT composite bed before splitting 11 area.That is, the area of the first sub- carbon nanotube layer 114 and the second sub- carbon nanotube layer 116 is substantially equal to The area of the carbon nanotube layer 110 before segmentation.
The separating method can be selected as needed, for example, using adhesive tape be attached to the first metal layer 120 and The surface of second metal layer 130, the adhesive tape is then pulled open again.The clamping devices such as tweezers can also be utilized, by the carbon nanometer Pipe composite bed 11 separates.Further, in the case where the thickness of CNT composite bed 11 meets condition, blade can also be used The CNT composite bed 11 is separated Deng cutting tool.In the present embodiment, by tearing the CNT composite bed 11 Mode to the CNT composite bed 11 apply directed force F, F '.
It is appreciated that a surface of the CNT composite bed 11 can also be fixed, and it is compound to the CNT The mode that another surface of layer 11 applies directed force F separates the CNT composite bed 11.
In step S122, during directed force F, F ' is continuously applied, carbon nanotube layer 110 is in directed force F, F ' Effect is lower to be separated, and forms the first sub- 114 and second sub- carbon nanotube layer 116 of carbon nanotube layer, and the first sub- carbon nanometer Tube layer 114 is attached at the surface of the first metal layer 120, and the dangling bonds by carbon nano tube surface and first metal Layer 120 combines;The second sub- carbon nanotube layer 116 is attached at the surface of the second metal layer 130, and passes through CNT The dangling bonds on surface and the surface of the second metal layer 130.During separation, the first sub- carbon nanotube layer 114 It is essentially identical with the thickness of the second sub- carbon nanotube layer 116, and be respectively uniformly distributed in the gold medal of the first metal layer 120 and second Belong to the surface of layer 130.CNT in the first sub- carbon nanotube layer 114 is basically parallel to the first metal layer 120 Surface, the CNT in the second sub- carbon nanotube layer 114 is basically parallel to the surface of the second metal layer 130.
The preparation method of collector provided in an embodiment of the present invention has advantages below:In the carbon by way of plating The surface of nanotube layer forms the first metal layer and second metal layer, and the first metal layer and second metal layer can be made firm The surface for being bonded to the carbon nanotube layer, so as to avoid the drift of CNT in subsequent applications or come off;The carbon is received Mitron layer can block metal level directly to be contacted with certain corrosive electrolyte, so as to prevent electrolyte and metal level it Between corrosion reaction, the metal level is not corroded, reduce corrosion product to connecing between collector and electrode material layer The influence of electric shock resistance;Furthermore because the carbon nanotube layer has good electric conductivity, and the carbon nanotube layer directly with it is described Electrode material layer is contacted and can preferably combined with the electrode material layer, so as to reduce further the collector and the electricity Contact resistance between the active material layer of pole;Finally, then the first metal layer and second metal layer are formed again by plating The mode torn, two collectors can be once prepared, so as to improve the preparation efficiency of the collector.
Also referring to Fig. 6, second embodiment of the invention provides a kind of preparation method of collector 10, including following step Suddenly:
Step S20 a, there is provided the first metal layer 120;
Step S21, there is provided a carbon nanotube layer 110, the carbon nanotube layer 110 include relative first surface 111 and Second surface 113, the first surface 111 of the carbon nanotube layer 110 is attached to the surface of the first metal layer 120;
Step S22, a second metal layer 130 is electroplated in the second surface 113 of the carbon nanotube layer 110, forms a carbon Nanotube composite bed 11;And
Step S23, the CNT composite bed 11 is torn, the carbon nanotube layer 110 is formed one first sub- carbon and receive Mitron layer 114 is attached at the surface of the first metal layer 120, and one second sub- CNT 116 is attached at described second layer by layer The surface of metal level 130.
The preparation method and first embodiment for the collector 10 that second embodiment of the invention provides are essentially identical, and its difference exists In now the first surface 111 of the carbon nanotube layer 110 and the first metal layer 120 being attached, then again in second surface 113 depositing second metal layers 130.
In the step s 21, the first metal layer 120 is combined closely with the carbon nanotube layer 110, first metal Layer 120 plays a part of the support carbon nanotube layer 110, and the thickness of the first metal layer 120 can be selected as needed Select, to support the carbon nanotube layer 10.In the present embodiment, the first metal layer 120 can be 10 microns, so that described Collector 10 has certain mechanical strength.
In step S22, during the deposition of the second metal layer 130, the second gold medal of the corresponding opening position of space 112 Category layer 130 will pass through the space 112 of the carbon nanotube layer 110, and is merged with the first metal layer 120, make institute Carbon nanotube layer 110 is stated to be firmly fixed between the first metal layer 120 and second metal layer 130.
In addition, those skilled in the art can also do other changes in spirit of the invention, these are according to present invention spirit The change done, it should all be included in scope of the present invention.

Claims (12)

1. a kind of preparation method of collector, including:
A carbon nanotube layer is provided, the carbon nanotube layer has relative first surface and second surface, the carbon nanotube layer Including multiple CNTs, at least part CNT is arranged at intervals to form multiple micropores;
A first metal layer is electroplated in the first surface of the carbon nanotube layer, is electroplated in the second surface of the carbon nanotube layer One second metal layer, form a CNT composite bed;And
The CNT composite bed is torn, the carbon nanotube layer is divided into the first sub- carbon nanotube layer along its thickness direction And the second sub- carbon nanotube layer, the first sub- carbon nanotube layer are attached at the surface of the first metal layer, second son Carbon nanotube layer is attached at the surface of the second metal layer.
2. the preparation method of collector as claimed in claim 1, it is characterised in that the carbon nanotube layer is a self-supporting knot Structure, it is made up of multiple CNTs, thickness direction of the multiple micropore along the carbon nanotube layer runs through the CNT Layer.
3. the preparation method of collector as claimed in claim 2, it is characterised in that correspond to micro well locations in electroplating process The first metal layer and second metal layer at place mutually merge to form integrative-structure.
4. the preparation method of collector as claimed in claim 2, it is characterised in that the first metal layer and second metal layer Electroplating process comprise the following steps:
One solution containing metal ion is provided;
The carbon nanotube layer is immersed in the solution, and and interval setting parallel with the electrode slice in solution, the carbon The first surface and second surface of nanotube layer are exposed in the metal ion solution;
An electrical potential difference is formed between the carbon nanotube layer and the electrode slice, makes metal ion reducing metal and electroplates in institute The first surface and second surface of carbon nanotube layer are stated, forms the first metal layer and second metal layer.
5. the preparation method of collector as claimed in claim 4, it is characterised in that the first metal layer is in the carbon nanometer The first surface of tube layer forms a continuous structure, and the second metal layer forms one in the second surface of the carbon nanotube layer Continuous structure.
6. the preparation method of collector as claimed in claim 4, it is characterised in that the carbon nanotube layer immerses metal ion In solution and the setting that suspends, the carbon nanotube layer in fixed frame are vacantly set.
7. the preparation method of collector as claimed in claim 1, it is characterised in that the carbon nanotube layer includes multilayer laminated And carbon nano-tube film arranged in a crossed manner, combined by Van der Waals force between the multilayer carbon nanotube film, each carbon nano-tube film It is arranged of preferred orient in the same direction including multiple CNTs, has one between the CNT in adjacent carbon nano-tube film Intersecting angle α, and the α is more than 0 degree and less than or equal to 90 degree.
8. the preparation method of collector as claimed in claim 1, it is characterised in that described along the CNT composite bed Thickness direction is torn the CNT composite bed and specifically included:
Two surface directions relative to the CNT composite bed apply the directed force F of opposite direction, F ';
It is continuously applied the institute firmly F, F ', the carbon nanotube layer in the CNT composite bed is separated from centre, paste respectively The surface of the first metal layer and second metal layer is invested, forms two collectors.
9. the preparation method of collector as claimed in claim 8, it is characterised in that the application direction of the directed force F is vertical In the first surface, the directed force F ' application direction perpendicular to the second surface.
10. the preparation method of collector as claimed in claim 8, it is characterised in that in the first sub- carbon nanotube layer Surface of the CNT parallel to the first metal layer;CNT in the second sub- carbon nanotube layer is parallel to described The surface of second metal layer.
11. a kind of preparation method of collector, including:
One the first metal layer is provided;
A carbon nanotube layer is provided, the carbon nanotube layer includes relative first surface and second surface, by the carbon nanometer The first surface of tube layer is attached at the surface of the first metal layer;
A second metal layer is electroplated in the second surface of the carbon nanotube layer, forms a CNT composite bed;And
The CNT composite bed is torn, the carbon nanotube layer is formed one first sub- carbon nanotube layer and is attached at described the The surface of one metal level, one second sub- CNT are attached at the surface of the second metal layer layer by layer, form two collectors.
12. the preparation method of collector as claimed in claim 11, it is characterised in that the mistake of the deposition of the second metal layer Cheng Zhong, correspond to the second metal layer at clearance position and run through the space of the carbon nanotube layer, and melt with the first metal layer It is combined.
CN201410269132.4A 2014-06-17 2014-06-17 The preparation method of collector Active CN105449221B (en)

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CN201410269132.4A CN105449221B (en) 2014-06-17 2014-06-17 The preparation method of collector
TW103123449A TWI508360B (en) 2014-06-17 2014-07-08 Method of making current collector
US14/738,955 US20150361573A1 (en) 2014-06-17 2015-06-15 Method of making current collector

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WO2019153273A1 (en) * 2018-02-09 2019-08-15 深圳前海优容科技有限公司 Battery, battery cell, and current collector and manufacturing method therefor
CN108539153B (en) * 2018-03-27 2022-10-14 电子科技大学 Metal lithium composite negative electrode material and preparation method thereof
CN109216703A (en) * 2018-09-06 2019-01-15 珠海光宇电池有限公司 A kind of flexible, porous collector and preparation method thereof
CN111048789B (en) * 2019-12-26 2023-01-24 珠海冠宇电池股份有限公司 Current collector and preparation method and application thereof
CN111900413B (en) * 2020-08-11 2021-09-28 珠海冠宇电池股份有限公司 Current collector and preparation method and application thereof

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CN103187573A (en) * 2011-12-28 2013-07-03 清华大学 Lithium-ion battery electrode
CN102738469A (en) * 2012-07-11 2012-10-17 中国第一汽车股份有限公司 Soft type polymeric compound lithium battery and preparation method thereof

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