CN114464813A - Lithium ion battery positive current collector, preparation method and lithium ion battery - Google Patents
Lithium ion battery positive current collector, preparation method and lithium ion battery Download PDFInfo
- Publication number
- CN114464813A CN114464813A CN202210079696.6A CN202210079696A CN114464813A CN 114464813 A CN114464813 A CN 114464813A CN 202210079696 A CN202210079696 A CN 202210079696A CN 114464813 A CN114464813 A CN 114464813A
- Authority
- CN
- China
- Prior art keywords
- pet
- current collector
- lithium ion
- ion battery
- positive electrode
- 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.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 55
- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 30
- 238000005886 esterification reaction Methods 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000011246 composite particle Substances 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003475 lamination Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 55
- 239000011148 porous material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 239000011888 foil Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 ethylene glycol modified graphene Chemical class 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a lithium ion battery anode current collector, a preparation method and a lithium ion battery. The positive current collector of the lithium ion battery has higher cohesive force and electronic conductivity, and ensures that the secondary battery has lower internal resistance, stable long-term circulation and higher safety performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery positive electrode current collector, a preparation method and a lithium ion battery.
Background
Lithium ion batteries have entered our daily lives with technological advances and increased environmental requirements. With the great popularization of lithium ion batteries, the safety problem caused by the fact that the lithium ion battery is punctured by external force occasionally occurs at a user end, the safety performance of the lithium ion battery is more and more emphasized by people, and particularly, continuous fermentation of some mobile phone explosion events causes new requirements on the safety performance of the lithium ion battery by users, after-sales terminals and lithium ion battery manufacturers.
At present, the method for improving the safety of the lithium ion battery is at the cost of sacrificing the energy density of the lithium ion battery, and therefore, a technical means capable of obviously improving the safety performance of the lithium ion battery under the condition of higher energy density is urgently needed. Patent No. 201922036027.7 provides a lithium ion battery positive pole current collector, including first aluminium layer and second aluminium layer and the plastics PET layer that is located first aluminium layer and second aluminium layer, this positive pole current collector uses is the intermediate layer aluminium foil, receives puncture or extrusion barrier film and pole piece when damaged at the battery, the intermediate layer aluminium foil can be stretched, because the PET tensile strength in the middle of the intermediate layer aluminium foil is greater than outer aluminium foil and leads to mainly being PET at the drawing in-process, it is PET also to pass barrier film and negative pole contact. The PET has excellent electrical insulation, so that the PET cannot cause internal short circuit of the battery when contacting with the cathode, and the thermal runaway of the battery is fundamentally avoided. Simultaneously, tensile PET also can wrap up on the surface of puncture foreign matter for the battery can not cause the battery short circuit because of the positive negative pole of foreign matter connection when the puncture foreign matter is the conductor, arouses the thermal runaway. Particularly, when the above action mechanism fails to avoid short circuit in the battery due to various reasons, because the aluminum metal layer outside the interlayer aluminum foil PET layer is much smaller than the thickness of the common aluminum foil, the aluminum foil is melted by a large amount of heat generated by a large current instantly when the aluminum foil is internally short-circuited, thereby interrupting the short circuit point to avoid thermal runaway caused by further heat generation of the battery, and in addition, the composite metal foil is lighter in weight than the pure metal foil 1/3-1/5, and the energy density of the battery level is increased.
The composite safe positive current collector can greatly improve the safety performance of the lithium ion battery, but has the following problems: 1) the PET and the metal of the composite foil have larger contact resistance, and simultaneously, due to the introduction of media such as flame retardants and the like, the resistance of the battery is increased, and the power of the battery is reduced; 2) the peeling strength between the positive membrane and the composite safe positive current collector is not large, and the membrane is easy to fall off powder in the long-term cycle process of the battery, so that the service life of the battery is influenced.
Disclosure of Invention
In view of the problems that the existing composite safe positive current collector technology can increase battery impedance and cause poor dynamics, the peeling strength between the current collector and a positive membrane is not large, and the long-term cycle life of the battery is influenced, the invention aims to provide a positive current collector of a lithium ion battery, wherein the positive current collector has higher cohesive force and electronic conductivity, and ensures that a secondary battery has lower internal resistance, and the battery has long-term cycle stability and higher safety performance.
In order to realize the purpose of the invention, the technical scheme is as follows: the utility model provides a lithium ion battery anodal mass flow body, includes first aluminium lamination and second aluminium lamination and is located PET layer between first aluminium lamination and the second aluminium lamination, the PET layer is latticed structure, comprises PET base member conducting agent.
Preferably, the conductive agent is one of acetylene black, ketjen black, graphene, carbon nanotubes, or any combination thereof. Due to the addition of the conductive agent, electrons can diffuse from the direction of the two-dimensional surface aluminum layer to the lug end, a passage is formed inside the PET substrate, the influence of electronic obstruction caused by the fracture of the surface aluminum layer caused by rolling is avoided, and the problem of poor conductivity of the composite safe positive current collector is greatly improved.
Preferably, the PET layer lattice structure is a circle, a diamond, a hexagon, or other regular polygon. The PET layer is arranged into a grid structure, so that anode compaction (part of materials are filled into gaps) is improved, lithium ions are migrated to a tab end through the two-dimensional direction of an aluminum layer on the surface of the current collector in comparison with the existing composite safe anode current collector, after the current collector is provided with through holes, the diffusion path of the lithium ions can be converted into three-dimensional all-dimensional penetration, the contact surface between the anode and cathode materials entering the gaps and the current collector is increased, the migration radius of the lithium ions is reduced, and the conductive efficiency is improved; in addition, the weight of the existing composite safe positive current collector is also reduced; moreover, the infiltration efficiency of the injected lithium battery electrolyte can be greatly improved, and the infiltration consistency can be ensured by 100%. In the existing lithium battery with the composite safe positive current collector, electrolyte is diffused and infiltrated from the longitudinal periphery to the center, and is in a three-dimensional type after being punched, so that the problem that part of the battery pole piece cannot be infiltrated in the center is thoroughly solved; more importantly, the surface adhesion of the current collector is improved, the surface aluminum layer of the existing safe composite positive current collector is smooth, the adhesion to the positive electrode diaphragm is small, the positive and negative electrode pole piece coating materials form an I-shaped occlusion state through the materials between the pores, the probability of falling off of the positive electrode diaphragm can be greatly reduced, and the service life of the battery is prolonged.
Preferably, the thickness of the first aluminum layer and the second aluminum layer is 1-2 μm, and the thickness of the PET layer is 8-14 μm.
Preferably, the porosity of the PET layer is 10-35%.
The second invention of the present invention is to provide a method for preparing the above lithium ion positive electrode current collector.
The invention also relates to a preparation method of the lithium ion battery anode current collector, which comprises the following steps:
s1, taking a PET monomer as a base material, adding an oxidation conductive agent modified by ethylene glycol into the base material to perform esterification reaction, wherein the oxidation conductive agent is one or any combination of acetylene black, Ketjen black, graphene and a carbon nano tube, and the PET monomer is terephthalic acid; the esterification reaction is also a polycondensation reaction;
s2, extruding and granulating the esterification reaction product prepared in the step S1 to form PET-based conductive composite particles;
s3, fusing the PET-based conductive composite particles on a 3D printer; setting parameters of the PET-based conductive composite film on a 3D printer; printing the molten PET-based conductive composite particles on a cooling roller through a spray head of the 3D printer to form a round, rhombic, hexagonal or other regular polygonal latticed structure film;
and S4, evaporating the first aluminum layer and the second aluminum layer to the PET-based conductive composite film in the step S4 by adopting a physical vapor deposition process to obtain the positive electrode current collector of the lithium ion battery.
Further, the S1 is performed in an N2 or Ar atmosphere.
Further, in the S1, the molar ratio of the ethylene glycol to the terephthalic acid is 1.2: 1-3.0: 1, the oxidation conductive agent accounts for 1-5% of the weight of the terephthalic acid, the esterification reaction is carried out at 230-260 ℃ for 4-6 hours, and the esterification reaction catalyst is tetrabutyl titanate, antimony trioxide or magnesium acetate.
Further, the 3D printer in step S3 further includes a winding mechanism.
The third invention of the present invention is to provide a lithium ion battery, comprising the above-mentioned lithium ion battery positive electrode current collector.
Compared with the prior art, the invention has the beneficial effects that:
1) the composite safe positive current collector with the same specification has the advantages that after the positive current collector is provided with the through holes, the weight is reduced, and the positive compaction is improved due to the fact that partial materials are filled into gaps and have the same surface density;
2) compared with the existing composite safe positive current collector, the lithium ion migration diffuses towards the lug end through the two-dimensional direction of the aluminum layer on the surface of the current collector, after the current collector is through-hole, the diffusion path of the lithium ion can be converted into three-dimensional all-dimensional penetration, and the contact surface between the positive and negative electrode materials entering the gap and the current collector is increased, so that the lithium ion migration radius is reduced, and the conductive efficiency is improved;
3) the infiltration efficiency of the lithium battery electrolyte after injection can be greatly improved, and the infiltration consistency can be ensured by 100%. In the existing lithium battery with the composite safe positive current collector, electrolyte is diffused and infiltrated from the longitudinal periphery to the center, and is in a three-dimensional type after being punched, so that the problem that part of the battery pole piece cannot be infiltrated in the center is thoroughly solved;
4) the surface adhesion of the current collector is improved, the surface aluminum layer of the existing safe composite positive current collector is smooth, the adhesion to the positive membrane is smaller, the positive and negative electrode plate coating materials form an I-shaped occlusion state through the materials among the pores, the falling probability of the positive membrane can be greatly reduced, and the service life of the battery is prolonged;
5) the added electrons of the conductive agent can be diffused to the lug end from the direction of the two-dimensional surface aluminum layer, a passage is also formed inside the PET substrate, the influence of electronic obstruction caused by the fracture of the surface aluminum layer due to rolling is avoided, and the problem of poor conductivity of the composite safe positive current collector is greatly improved.
Drawings
FIG. 1: the structure of the positive current collector of the lithium ion battery is schematically shown;
FIG. 2: the invention discloses a structural schematic diagram of a positive current collector PET layer of a lithium ion battery;
FIG. 3: peeling strength curve graphs of the positive electrode films of examples 1-3 and comparative examples of the invention;
FIG. 4: internal resistance histograms of the cells of examples 1-2 of the invention and comparative examples;
FIG. 5: high temperature cycling profiles for inventive examples 1-2 and comparative examples.
In the figure: 1-a first aluminum layer; 2-a second aluminum layer; 3-PET layer.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings, specific embodiments and comparative examples. It is to be understood that the specific embodiments described in this specification are for purposes of explanation only and are not to be construed as limitations of the present invention, but rather are provided for enabling a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.
The first aspect of the invention provides a lithium ion battery anode current collector:
for solving the problems of poor conductivity, large internal resistance, small peeling strength of a positive diaphragm and the like of the lithium ion battery manufactured by the existing composite safe positive current collector, the positive current collector of the lithium ion battery shown in fig. 1 and 2 comprises a first aluminum layer 1, a second aluminum layer 2 and a PET layer 3 positioned between the first aluminum layer 1 and the second aluminum layer 2, wherein the PET layer 3 is of a grid-shaped structure and consists of a PET base body and a conductive agent.
The grid-shaped structure is preferably selected from a circle, a diamond, a hexagon or other regular polygons; the conductive agent is one or any combination of acetylene black, Ketjen black, graphene and carbon nanotubes.
The thickness of the first aluminum layer and the second aluminum layer is 1-2 μm, but not limited to 1 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.6 μm, 1.8 μm or 2.0 μm. The thickness of the PET layer is 8-14 μm, and can be selected from but not limited to 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm. The porosity of the PET layer is 10-35%, and can be selected from but not limited to 10%, 15%, 20%, 25%, 30% or 35%.
The second aspect of the present invention provides a method for preparing the positive electrode current collector of the lithium ion battery, comprising:
a method for preparing the positive electrode current collector of the lithium ion battery comprises the following steps:
s1, taking a PET monomer as a base material, adding an oxidation conductive agent modified by ethylene glycol into the base material to perform esterification reaction, wherein the conductive agent is one or any combination of acetylene black, Ketjen black, graphene and a carbon nano tube, and the PET monomer is terephthalic acid;
s2, extruding and granulating the esterification reaction product prepared in the step S1 to form PET-based conductive composite particles;
s3, fusing the PET-based conductive composite particles on a 3D printer; setting parameters of the PET-based conductive composite film on a 3D printer; printing the molten PET-based conductive composite particles on a cooling roller through a spray head of the 3D printer to form a circular, rhombic, hexagonal or other regular polygonal latticed structure film; specifically, parameters of the PET-based conductive composite film, such as film thickness, pore size, pore shape, and pore distribution, can be set by a 3D printer, typically with a film thickness of 6 to 12 μm and a pore size of less than 20 μm, and with a pore shape such as any regular polygon described in the first aspect of the present invention.
And S4, evaporating the first aluminum layer and the second aluminum layer to the PET-based conductive composite film in the step S4 by adopting a physical vapor deposition process to obtain the positive electrode current collector of the lithium ion battery. The thickness of the first aluminum layer and the second aluminum layer obtained in the step is 1-2 mu m, the thickness of the PET-based conductive composite film is 8-14 mu m, and the porosity is 10-35%.
In order to uniformly disperse the oxidized conductive agent in the PET monomer as much as possible, the step S1 is carried out in an N2 or Ar atmosphere, the molar ratio of the ethylene glycol to the terephthalic acid is 1.2: 1-3.0: 1, the conductive agent accounts for 1-5% of the terephthalic acid by weight, esterification reaction is carried out at 230-260 ℃ for 4-6 hours, and the esterification reaction catalyst is tetrabutyl titanate or antimony trioxide or magnesium acetate. The esterification reaction in this example is also a polycondensation reaction.
Further, the 3D printer in step S3 further includes a winding mechanism that winds the manufactured PET-based conductive composite film.
A third aspect of the present invention provides a lithium ion battery:
the lithium ion battery of the embodiment comprises the lithium ion battery anode current collector.
Next, specific examples are provided according to aspects of the first, second, and third aspects of the present invention.
Example 1
The lithium ion battery anode current collector:
weighing 50g of graphene oxide powder, adding the graphene oxide powder into 6L of ethylene glycol solution, and performing ultrasonic oscillation for 2 hours to obtain ethylene glycol modified graphene oxide suspension; adding the prepared ethylene glycol modified graphene oxide suspension, 5kg of terephthalic acid and 1.5g of trimethyl phosphate serving as an esterification reaction stabilizer and 1.5g of tetrabutyl titanate serving as a catalyst (wherein the molar ratio of the ethylene glycol to the terephthalic acid is 3:1) into a reaction kettle, continuously introducing N2/Ar at the speed of 20mL/min, heating and stirring to perform an esterification reaction at the reaction temperature of 250 ℃ for 4 hours to obtain an initial product; raising the temperature to 280 ℃, and simultaneously vacuumizing and curing to obtain a prepolymer; and (3) feeding the prepared polycondensation reaction prepolymer into a double-screw extruder for extrusion granulation to form the PET-based conductive composite particles.
Fusing the PET-based conductive composite particles on a 3D printer; further, a 3D printer was provided with a desired PET porous film having a thickness of 6 μm and a pore diameter of 15 μm, and a square shape and a porosity of 20% (porosity: void volume/solid volume); printing the molten PET-based conductive composite particles on a cooling roller through a spray head of a 3D printer, and rolling to obtain a latticed structure film; and evaporating the first aluminum layer and the second aluminum layer on the PET-based conductive composite film by adopting a physical vapor deposition process to obtain the lithium ion battery anode current collector with the thickness of the aluminum layers on both sides being 1 mu m.
Example 2
Weighing 450g of graphene oxide powder, adding the graphene oxide powder into 6L of ethylene glycol solution, and performing ultrasonic oscillation for 2 hours to obtain ethylene glycol modified graphene oxide suspension; adding the prepared ethylene glycol modified graphene oxide suspension, 10kg of terephthalic acid and 1.2g of phosphorous acid serving as an esterification reaction stabilizer and 1.8g of antimony trioxide serving as a catalyst (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1) into a reaction kettle, continuously introducing N2/Ar at the speed of 20mL/min, heating and stirring to perform an esterification reaction at the reaction temperature of 230 ℃ for 6 hours to obtain an initial product; raising the temperature to 280 ℃, and simultaneously vacuumizing and curing to obtain a prepolymer; and (3) feeding the prepared polycondensation reaction prepolymer into a double-screw extruder for extrusion granulation to form the PET-based conductive composite particles.
Fusing the PET-based conductive composite particles on a 3D printer; further, a 3D printer was provided with a desired PET porous film having a thickness of 8 μm and a pore diameter of 8 μm and a pore shape of rhombohedral and a porosity of 10% (porosity ═ void volume/solid volume); printing the molten PET-based conductive composite particles on a cooling roller through a spray head of a 3D printer, and rolling to obtain a latticed structure film; and evaporating the first aluminum layer and the second aluminum layer on the PET-based conductive composite film by adopting a physical vapor deposition process to obtain the lithium ion battery anode current collector with the thicknesses of the aluminum layers on the two sides being 2 microns.
Example 3
Weighing 200g of graphene oxide powder, adding the graphene oxide powder into 8L of ethylene glycol solution, and performing ultrasonic oscillation for 2 hours to obtain ethylene glycol modified graphene oxide suspension; adding the prepared ethylene glycol modified graphene oxide suspension, 10kg of terephthalic acid and 1.5g of trimethyl phosphate serving as an esterification reaction stabilizer and 1.5g of ethylene glycol antimony serving as a catalyst (wherein the molar ratio of ethylene glycol to terephthalic acid is 1.5:1) into a reaction kettle, continuously introducing N2/Ar at the speed of 20mL/min, heating and stirring to perform an esterification reaction at the reaction temperature of 250 ℃ for 5 hours to obtain a primary product; raising the temperature to 280 ℃, and simultaneously vacuumizing and curing to obtain a prepolymer; and (3) feeding the prepared polycondensation reaction prepolymer into a double-screw extruder for extrusion granulation to form the PET-based conductive composite particles.
Fusing the PET-based conductive composite particles on a 3D printer; further, a desired PET porous film having a thickness of 12 μm and a pore diameter of 100nm and a pore shape of a circle and a porosity of 30% (porosity ═ void volume/solid volume) was set on a 3D printer; printing the molten PET-based conductive composite particles on a cooling roller through a spray head of a 3D printer, and rolling to obtain a latticed structure film; and evaporating the first aluminum layer and the second aluminum layer on the PET-based conductive composite film by adopting a physical vapor deposition process to obtain the lithium ion battery anode current collector with the thickness of the aluminum layers on both sides being 1 mu m.
Comparative examples 1 to 2
8 μm (Al-1 μm/PET-6 μm/Al-1 μm) and 14 μm (Al-1 μm/PET-12 μm/Al-1 μm) composite safety positive electrode current collectors purchased from Jiangyin XX X New Material science Co.
Preparing a lithium ion battery:
and (3) uniformly coating the positive electrode slurry containing the active material, the conductive agent and the binder on two sides of the lithium ion positive electrode current collector in the embodiment 1-3 and the comparative example 1-2 by using a coating machine, rolling, splitting, welding a tab, assembling and winding with a negative electrode plate and an isolating film, then packaging into an aluminum foil packaging bag, baking at 85 ℃ to remove water, injecting a non-aqueous electrolyte, sealing, forming, exhausting and testing the capacity to obtain the finished lithium ion battery. The lithium cobalt oxide, the negative graphite and the commercial 4.45V electrolyte for preparing the lithium battery anode material are used, and the lithium battery material system is not limited in the invention.
The positive electrode sheets obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to a peeling force test, the positive electrode sheet was bonded to a stainless steel plate to be tested with a 3M strong double-sided tape (VHB), the positive electrode sheet was peeled off in a 180 ° direction with a tensile machine at a peeling rate of 200mm/min for 5 sheets/sample, and the results of the test are shown in table 1 and fig. 3.
As can be seen from table one and fig. 3, the peel strength of the PET-based conductive composite film positive electrode film sheet with the grid-shaped structure is significantly greater than that of the comparative example.
Further, the batteries prepared in examples 1 and 2 and comparative examples 1 and 2 were tested, and the results are shown in table 2, fig. 4, and fig. 5.
Watch two
As can be seen from the second table and FIG. 4, the internal resistance of the positive membrane of the PET-based conductive composite film with the grid structure is obviously smaller than that of the comparative example group, the high-temperature circulation capacity at 45 ℃ of 1C/1C keeps the advantages of the example group and the comparative example group, and 100% needling, extrusion and weight impact passing can be ensured.
It should be noted that the battery testing method of the present invention:
1. testing the internal resistance of the battery: and a battery internal resistance tester with the frequency of 1 KHZ.
2. In an oven at 45 ℃, 4.45V was charged at 1C, current was cut off at 0.05C, and discharged to 3.0V, with a capacity retention rate of 100% discharge capacity/initial discharge capacity.
3. Performing a needling experiment, fully charging a sample at a current of 0.5 ℃, standing for 1h, and measuring the voltage and the internal resistance of a battery; vertically penetrating a steel nail with the diameter of 2.5-3.5 mm through the center of the battery cell, keeping the steel nail for more than 15min, and recording the temperature of the surface of the battery; and after the test is finished, standing for 1h, and measuring the voltage and the internal resistance of the battery. And (3) judging standard: no fire and explosion, and the highest temperature of the surface of the battery core is less than or equal to 150 ℃.
4. A squeezing experiment, charging to a limit voltage at a given charging current of 0.5C, changing to constant voltage charging when the battery voltage reaches the limit voltage, until the charging current is less than or equal to a given cutoff current of 0.05C; standing for 1h, and measuring OCV and internal resistance; the electric core bears extrusion between two planes, the extrusion pressure is provided by a hydraulic oil cylinder, the extrusion is continued until the pressure reading of the hydraulic oil cylinder reaches 17.2Mpa (the pressure is 13kN), the maximum pressure is reached, and the pressure is released immediately; 1h after the test, the OCV and the internal resistance of the battery were measured.
When the cylindrical or square battery cell is extruded, the long axis of the battery cell is parallel to the plane of the extrusion device (horizontal), the square battery cell is required to rotate 90 degrees (vertical) along the long axis, and each battery only bears one extrusion.
And (3) judging standard: without fire or explosion
5. The heavy object is impacted, the battery is charged to the limit voltage at the given charging current of 0.5C, when the battery voltage reaches the limit voltage, the battery is charged at a constant voltage until the charging current is less than or equal to the given cutoff current of 0.02C; standing for 1h, and measuring OCV and internal resistance; placing the battery core on a plane, transversely placing a rod with the diameter of 15.8mm at the center of the battery core, and allowing an iron block weighing 9.1kg to fall onto the rod from a position with the height of 610 mm; after standing for 1h, the OCV and the internal resistance of the battery were measured.
The long axis of the battery is parallel to the plane of impact (the largest cell) and perpendicular to the iron rod placed in the center of the battery, and a different battery is used for each impact.
And (3) judging standard: no fire and explosion.
Those skilled in the art to which the present application pertains can also make appropriate changes and modifications to the above-described embodiments, based on the disclosure of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application. Finally, the above examples are intended only to illustrate the technical solution of the present invention and not to limit it, and although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention defined by the appended claims.
Claims (10)
1. The utility model provides a lithium ion battery anodal mass flow body, includes first aluminium lamination and second aluminium lamination and is located the PET layer between first aluminium lamination and the second aluminium lamination, its characterized in that: the PET layer is of a grid-shaped structure and consists of a PET matrix and a conductive agent.
2. The positive electrode current collector of claim 1, wherein: the conductive agent is one or any combination of acetylene black, Ketjen black, graphene and carbon nanotubes.
3. The positive electrode current collector of claim 1, wherein: the latticed structure of the PET layer is a circle, a diamond, a hexagon or other regular polygons.
4. The positive electrode current collector of claim 1, 2 or 3, wherein: the thickness of the first aluminum layer and the second aluminum layer is 1-2 μm, and the thickness of the PET layer is 8-14 μm.
5. The positive electrode current collector of claim 4, wherein: the porosity of the PET layer is 10-35%.
6. A method for preparing the positive electrode current collector of the lithium ion battery as claimed in any one of claims 1 to 5, comprising the steps of:
s1, taking a PET monomer as a base material, adding an oxidation conductive agent modified by ethylene glycol into the base material to perform esterification reaction, wherein the oxidation conductive agent is one or any combination of acetylene black, Ketjen black, graphene and a carbon nano tube, and the PET monomer is terephthalic acid;
s2, extruding and granulating the esterification reaction product prepared in the S1 to form PET-based conductive composite particles;
s3, fusing the PET-based conductive composite particles on a 3D printer; setting parameters of the PET-based conductive composite film on a 3D printer; printing the molten PET-based conductive composite particles on a cooling roller through a spray head of the 3D printer to form a round, rhombic, hexagonal or other regular polygonal latticed structure film;
and S4, evaporating the first aluminum layer and the second aluminum layer to the two sides of the PET-based conductive composite film in the step S4 by adopting a physical vapor deposition process to obtain the positive electrode current collector of the lithium ion battery.
7. The method of preparing a positive current collector for a lithium ion battery of claim 6, wherein: the S1 was performed in N2 or Ar atmosphere.
8. The method of preparing a positive current collector for a lithium ion battery of claim 6, wherein: the molar ratio of the ethylene glycol to the terephthalic acid in the S1 is 1.2: 1-3.0: 1, the oxidation conductive agent accounts for 1-5% of the weight of the terephthalic acid, esterification reaction is carried out at 230-260 ℃ for 4-6 hours, and the esterification reaction catalyst is tetrabutyl titanate or antimony trioxide or magnesium acetate.
9. The method of preparing a positive electrode current collector for a lithium ion battery according to claim 6, 7 or 8, wherein: and the 3D printer in the S3 further comprises a winding mechanism.
10. A lithium ion battery, characterized by: comprising the lithium ion battery positive electrode current collector of claims 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210079696.6A CN114464813A (en) | 2022-01-24 | 2022-01-24 | Lithium ion battery positive current collector, preparation method and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210079696.6A CN114464813A (en) | 2022-01-24 | 2022-01-24 | Lithium ion battery positive current collector, preparation method and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114464813A true CN114464813A (en) | 2022-05-10 |
Family
ID=81412459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210079696.6A Pending CN114464813A (en) | 2022-01-24 | 2022-01-24 | Lithium ion battery positive current collector, preparation method and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114464813A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695900A (en) * | 2022-05-31 | 2022-07-01 | 江苏卓高新材料科技有限公司 | Composite current collector, positive pole piece and preparation method of positive pole piece |
| CN115148508A (en) * | 2022-08-08 | 2022-10-04 | 凌容新能源科技（上海）股份有限公司 | Energy storage capacitor and preparation method thereof |
| CN115425234A (en) * | 2022-08-29 | 2022-12-02 | 浙江柔震科技有限公司 | Composite current collector and preparation method thereof |
| WO2023239312A1 (en) * | 2022-06-09 | 2023-12-14 | İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. | Thermoplastic based composite single-layer cathode used in secondary batteries |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068972A (en) * | 2017-03-22 | 2017-08-18 | 江苏元景锂粉工业有限公司 | The ternary material anode pole piece and its lithium ion battery of a kind of quick charge |
| US20190267634A1 (en) * | 2016-04-07 | 2019-08-29 | Rutgers, The State University Of New Jersey | Electrochemical devices and methods for making same |
| CN111129505A (en) * | 2020-01-21 | 2020-05-08 | 合肥国轩高科动力能源有限公司 | Lithium battery using light current collector |
| CN210837945U (en) * | 2019-11-22 | 2020-06-23 | 芜湖天弋能源科技有限公司 | Lithium ion battery |
-
2022
- 2022-01-24 CN CN202210079696.6A patent/CN114464813A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190267634A1 (en) * | 2016-04-07 | 2019-08-29 | Rutgers, The State University Of New Jersey | Electrochemical devices and methods for making same |
| CN107068972A (en) * | 2017-03-22 | 2017-08-18 | 江苏元景锂粉工业有限公司 | The ternary material anode pole piece and its lithium ion battery of a kind of quick charge |
| CN210837945U (en) * | 2019-11-22 | 2020-06-23 | 芜湖天弋能源科技有限公司 | Lithium ion battery |
| CN111129505A (en) * | 2020-01-21 | 2020-05-08 | 合肥国轩高科动力能源有限公司 | Lithium battery using light current collector |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695900A (en) * | 2022-05-31 | 2022-07-01 | 江苏卓高新材料科技有限公司 | Composite current collector, positive pole piece and preparation method of positive pole piece |
| WO2023239312A1 (en) * | 2022-06-09 | 2023-12-14 | İzmi̇r Eği̇ti̇m Sağlik Sanayi̇ Yatirim A.Ş. | Thermoplastic based composite single-layer cathode used in secondary batteries |
| CN115148508A (en) * | 2022-08-08 | 2022-10-04 | 凌容新能源科技（上海）股份有限公司 | Energy storage capacitor and preparation method thereof |
| CN115425234A (en) * | 2022-08-29 | 2022-12-02 | 浙江柔震科技有限公司 | Composite current collector and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114464813A (en) | Lithium ion battery positive current collector, preparation method and lithium ion battery | |
| CN113078282A (en) | Positive plate and lithium ion battery | |
| WO2017190584A1 (en) | Secondary battery of zinc-lithium-manganese water system and preparation method therefor | |
| CN109980290B (en) | Mixed solid-liquid electrolyte lithium storage battery | |
| CN115066767A (en) | Positive plate and lithium ion battery | |
| CN114824260A (en) | Safety lithium ion battery | |
| CN114373887A (en) | Lithium ion battery, lithium ion battery positive plate and preparation method thereof | |
| CN114824259A (en) | Lithium ion battery composite positive plate, preparation method thereof and lithium ion battery | |
| CN114497566A (en) | Positive plate and lithium ion battery | |
| CN110611102A (en) | Current collector, pole piece, preparation method of pole piece and electrochemical energy storage device | |
| CN114204038A (en) | Current collector and application thereof | |
| CN117169058A (en) | Determination method for wettability of lithium ion battery | |
| CN113140702A (en) | Silicon-based negative electrode plate with sandwich structure and preparation method and application thereof | |
| CN114512633B (en) | Negative plate and battery comprising same | |
| CN114512670B (en) | Negative plate and battery comprising same | |
| CN116169366A (en) | Solid-state lithium battery, preparation method thereof and electric equipment | |
| CN213936246U (en) | Positive pole piece of lithium ion battery | |
| CN214428670U (en) | Lithium ion battery capable of being charged at low temperature | |
| CN113675370A (en) | Positive plate and lithium ion battery | |
| CN114864952A (en) | Battery core, battery module and battery pack | |
| CN113594411A (en) | Positive plate and battery | |
| CN218783056U (en) | Positive pole piece structure with high specific energy and high safety | |
| CN113471401B (en) | High-safety high-load lithium ion electrode plate and manufacturing method thereof | |
| CN220526953U (en) | Pole piece, battery and electricity utilization device | |
| CN217158233U (en) | Positive plate of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |