CN108550859A - Porous current collector and preparation method thereof and lithium battery - Google Patents
Porous current collector and preparation method thereof and lithium battery Download PDFInfo
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- 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
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- 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
- H01M4/70—Carriers or collectors characterised by shape or form
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- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Porous current collector and preparation method thereof and lithium battery, the porous current collector include the collector matrix for having pore space structure, and collector matrix surface and internal surface of hole are attached with solid electrolyte layer, and solid electrolyte layer is at least one layer.Using the porous current collector as the cathode pole piece of lithium battery, without filling electrode active material on cathode pole piece, the present invention uses three-dimensional porous collector, and adhere to solid electrolyte layer in collector matrix surface and hole, the lithium that collector intrinsic silicon deposits when having big quantity space that can accommodate lithium battery charging, during lithium is deposited repeatedly with deviating from, the volume of collector itself remains unchanged, reduce lithium metal volume in cyclic process and changes the adverse effect brought repeatedly, solid electrolyte layer can inhibit the formation of Li dendrite simultaneously, improve the cycle performance of lithium battery.The present invention does not use lithium metal directly when battery makes, and does not need harsh environmental Kuznets Curves, reduces the cost of manufacture of lithium battery.
Description
Technical field
The invention belongs to technical field of lithium batteries more particularly to a kind of collector of porous structure and preparation method thereof and lithiums
Battery.
Background technology
In recent years, with the fast development of portable electronic device, electric vehicle, power grid energy storage technology, people are to high energy
The demand of metric density, the battery of high security and energy-storage system is more and more urgent.In commercialized electrochemical energy storage device
In, lithium ion battery becomes the optimal selection of people because having many advantages, such as that energy density is high, having extended cycle life.However, by
The limitation of electrode material, the progress for how further increasing lithium ion battery energy density are more slow.
Graphite is current most widely used lithium ion battery negative material, but its theoretical capacity is only 372mAh/g, more
To be more difficult to meet the needs of people are to high energy density cells.Compared to graphite cathode, the theoretical capacity of lithium an- ode is bright
Aobvious higher, reaches 3860mAh/g；And metal lithium electrode has most negative potential, reaches -3.040V (vs. standard hydrogen electrodes).
Therefore it is expected to realize large-scale application in future using the battery of lithium an- ode.However, using the lithium battery of lithium an- ode
There is also some intrinsic defects.Currently, the maximum cycle for hindering to be lithium metal of application of the lithium an- ode on battery
Stability and safety.In lithium battery cyclic process, lithium ion is deposited and is detached from lithium metal surface repeatedly, is easily caused
Lithium metal surface smoothness declines and current density is unevenly distributed, and then forms Li dendrite, brings security risk.And in lithium
During ion deposition and abjection, lithium metal volume is expanded and is shunk repeatedly, and the original SEI films in lithium metal surface is caused to destroy,
Constantly there are new SEI films to be formed simultaneously, causes the serious consumption of electrolyte and active lithium, lithium battery cycle performance is caused quickly to decline
Subtract.If the lithium of deposition is detached from lithium metal surface and forms " dead lithium ", the cycle performance of battery can be made to further decrease.In addition,
It, must be stringent in battery manufacturing process if directly doing cathode using lithium metal since lithium metal chemical property is very active
Environment temperature and humidity are controlled, this is undoubtedly increased manufacturing cost.
If not using lithium an- ode directly when lithium battery manufactures, from the lithium ion energy of anode abjection when battery works
Enough reversibly deposition and abjections on negative current collector, then no longer need harsh environmental Kuznets Curves in battery manufacturing process, can be bright
It is aobvious to reduce manufacture difficulty, reduce manufacturing cost.In this regard, scientist has done some explorations, such as exploitation is with LiFePO4For positive material
Material, using copper as negative current collector, and fill the electrolyte containing high concentration lithium salts without negative pole lithium battery [Advanced
Functional Materials, 2016,26,7094-7102], however the cycle performance of the battery or not ideal enough.In order to
Reduce lithium metal volume in cyclic process and change the adverse effect brought repeatedly, inhibit the formation of Li dendrite, improves lithium battery
Cycle performance, reduce the cost of manufacture of lithium battery, exploitation new current collector is an important research direction.
In recent years, the collector with three-dimensional porous structure causes more extensive concern.Have in such collector
Electrode active material is filled in afflux body opening and electrode is made by interconnected hole.The ionic conduction and electronics of such electrode
Conduction is respectively formed three-dimensional path, is better than traditional coated electrode, the utilization rate of electrode active material theoretically can be improved, and inhibit
Volume expansion of the electrode in cyclic process.Such as the Chinese invention patent of Patent No. 201210158278.2, Patent No.
201210433799.4 Chinese invention patent, the Chinese invention patent of Patent No. 201210081945.1, Patent No.
201210433237.X Chinese invention patent, application No. is 201210082241.6 Chinese invention patent application, application numbers
Chinese invention patent application for 201210413033.X and the Chinese invention patent Shen application No. is 201510117274.3
It please wait the electrode disclosed using three-dimensional collector, the common ground of these electrodes is to use porous current collector, and by electrode active
Property material fill to afflux body opening, with reach to be formed sufficient conductive network, efficiently utilize active material and inhibitory activity material
Expect the purpose of volume expansion in cyclic process.However, the way for filling active material in afflux body opening increases active material
With the area of electrolyte contacts, more electrodes can be brought --- electrolyte interface side reaction；And to active material cyclic process
The inhibiting effect of middle volume expansion only reserves enough expandable spaces before circulating battery for active material.It is prior
It is, although in electrode fabrication process active material, active material actually filling out in afflux body opening can be added according to predetermined amount
Charge is difficult to control, and is not filled effectively by active material in big quantity space in afflux body opening memory, i.e., is in afflux body opening
Space needed for the expansion practical much larger than active material of the reserved space of active material expansion, the actual space availability ratio of collector
Relatively low, the electrode consistency that different batches make also is difficult to ensure.These defects are caused three-dimensional collector and active material
Material simply in conjunction with method cannot improve battery energy density and cycle life in a desirable manner.
Invention content
The purpose of the present invention is to provide a kind of at low cost and can inhibit Li dendrite and formed and improve cycle performance of battery
Porous current collector and preparation method thereof and lithium battery.
To achieve the goals above, the present invention takes following technical solution：
Porous current collector, includes the collector matrix with pore space structure, table in the collector matrix surface and hole
Face is attached with solid electrolyte layer, and the solid electrolyte layer is at least one layer.
Further, the solid electrolyte layer contains polymer and lithium salts.
Further, the polymer is polyvinyl alcohol, polyethylene glycol oxide, Kynoar, Kynoar-hexafluoro
Propylene copolymer, alkylated I oxide, polyvinylpyrrolidone, polyvinyl butyral, hydroxyethyl cellulose, methyl
Hydroxyethyl cellulose, sodium carboxymethylcellulose, cellulose acetate propionate, polyacrylamide, polymethyl methacrylate, poly- methyl
Butyl acrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-acetate ethylene copolymer, polyvinyl acetate, polyurethane, three
Melamine-formaldehyde, urea-formaldehyde, maleic anhydride and its derivative and the copolymer of esters, makrolon, gather polyacrylonitrile
At least one of siloxanes, gelatin, starch；Or the polymer is containing polyvinyl alcohol, polyethylene glycol oxide, polyvinylidene fluoride
Alkene, Kynoar-hexafluoropropylene copolymer, alkylated I oxide, polyvinylpyrrolidone, polyvinyl alcohol contracting fourth
Aldehyde, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, cellulose acetate propionate, polyacrylamide, gathers hydroxyethyl cellulose
Methyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-acetate ethylene copolymer, gathers polybutyl methacrylate
Vinylacetate, polyurethane, melamino-formaldehyde, urea-formaldehyde, maleic anhydride and its derivative and the copolymer of esters,
At least two copolymer in polyacrylonitrile, makrolon, polysiloxanes.
Further, the lithium salts is LiClO4、LiPF6Or Rf replaces part F-, LiBF4Or Rf replaces part F-、
LiAsF6Or Rf replaces part F-、LiSbF6Or Rf replaces part F-、LiB(C2O4)2、LiCF3SO3、LiCnF2n+1SO3(n≥2)、
LiC(CF3SO2)3、LiC(CnF2n+1SO2)3、LiCF3CO2、LiCnF2n+1CO2(n≥2)、LiC2F4(SO3)2、LiN(FSO2)2、LiN
(CF3SO2)2、LiN(C2F5SO2)2、LiN(CnF2n+1SO2)2、LiN(RfOSO2)2At least one of.
Further, the solid electrolyte layer contains inorganic filler, and the quality of the inorganic filler accounts for solid electrolyte
The 0%~80% of layer gross mass.
Further, the inorganic filler be lithium metasilicate, lithium borate, lithium phosphate, lithium carbonate, aluminium oxide lithium, titanium oxide lithium,
Lanthana lithium, aluminum phosphate lithium, aluminum phosphate titanium lithium, aluminum phosphate germanium lithium, zirconic acid lanthanum lithium, silica, magnesia, aluminium oxide, calcium oxide,
Strontium oxide strontia, barium monoxide, titanium oxide, zirconium oxide, gallium oxide, tin oxide, calcium sulfate, strontium sulfate, barium sulfate, calcium carbonate, strontium carbonate,
At least one of barium carbonate, aluminium hydroxide.
Further, the thickness of the collector matrix is 1 μm~2000 μm.
Further, the thickness of the solid electrolyte layer is 0.01 μm~30 μm.
The preparation method of previous porous collector, includes the following steps：
Polymer, lithium salts are added in solvent and are mixed, solution is made after stirring evenly；
Solution obtained is coated on collector matrix, or collector matrix is put into impregnate in solution obtained and is taken
Go out；
Collector matrix is dried, collector matrix surface is obtained and internal surface of hole is attached with solid electrolyte layer
Porous current collector.
The preparation method of previous porous collector, includes the following steps：
Polymer, lithium salts are added in solvent and carry out being mixed and made into solution, inorganic filler is added into solution, stirs evenly
Suspension is made；
Suspension obtained is coated on collector matrix, or collector matrix is put into suspension obtained and is soaked
It is taken out after bubble；
Collector matrix is dried, collector matrix surface is obtained and internal surface of hole is attached with solid electrolyte layer
Porous current collector.
Further, the quality of the polymer accounts for the 4~6% of solution gross mass, and it is total that the quality of the lithium salts accounts for solution
The 1.5~2.5% of quality.
Further, the quality of the polymer accounts for the 4~6% of solution gross mass, and it is total that the quality of the lithium salts accounts for solution
The 1.5~2.5% of quality, the quality of the inorganic filler account for the 0.9~11% of suspension gross mass.
Further, the solid electrolyte layer of the collector matrix surface and internal surface of hole have two layers or two layers with
When upper, the constituent of the solid electrolyte layer of adjacent two layers is not exactly the same, the solid not being in direct contact with collector matrix
Electrolyte layer contains polymer, or contains polymer and lithium salts and/or inorganic filler.
Lithium battery, including anode pole piece, cathode pole piece and diaphragm, the cathode pole piece are using previous porous collector
Porous current collector made from preparation method is not filled with electrode active material on the cathode pole piece.
By above technical scheme it is found that being different from traditional two-dimentional foil collector, the present invention is by three-dimensional porous collector
Applied to the cathode of lithium battery, since hole inner wall has certain curvature, the lithium of anode abjection is in three-dimensional porous collector inner hole deposition
When product, Li dendrite can in all directions be grown in three dimensions, largely reduce the growth perpendicular to collector direction,
The probability for piercing through diaphragm is reduced, additionally due to solid electrolyte layer has good mechanical strength, Li dendrite can be inhibited to be formed,
It further reduced security risk；Moreover, different from existing porous current collector merely using polymer as binder or clad
Scheme, the present invention forms the solid electrolytic without electrode active material in three-dimensional porous collector matrix surface and internal surface of hole
Matter layer contains lithium salts in solid electrolyte layer, to which collector matrix and solid electrolyte layer constitute complete electrode, lithium
Lithium ion in salt is deposited in a metallic form between collector matrix and solid electrolyte layer, can improve lithium ion conductance
Rate, it is ensured that lithium ion is improved in three-dimensional porous collector matrix surface and more successfully deposition and the abjection of matrix internal surface of hole
The cycle performance of lithium battery.Because not using lithium metal directly when battery makes, harsh environmental Kuznets Curves are not needed, the present invention is also
The cost of manufacture of lithium battery can be reduced.
Specific implementation mode
In order to which above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention cited below particularly,
It is described below in detail.
The present invention has the collector of through-hole structure as collector matrix using such as nickel foam, foam copper, in afflux
Body matrix surface and internal surface of hole adhere to solid electrolyte layer.The thickness of collector matrix can be 1 μm~2000 μm, solid electricity
The thickness for solving matter layer can be 0.01 μm~30 μm.It is attached to the solid electrolyte layer of collector matrix surface and internal surface of hole extremely
It is one or more layers less.
Contain polymer and lithium salts in the solid electrolyte layer of the present invention.The polymer has after being dissolved in nitrile equal solvent
Have compared with high viscosity, and hardness is little after solid electrolyte layer drying, and there is certain tensile strength, polymer of the invention
Can be polyvinyl alcohol, polyethylene glycol oxide, Kynoar, Kynoar-hexafluoropropylene copolymer, alkylated I
Oxide, polyvinylpyrrolidone, polyvinyl butyral, hydroxyethyl cellulose, methyl hydroxyethylcellulose, carboxymethyl cellulose
Plain sodium, cellulose acetate propionate, polyacrylamide, polymethyl methacrylate, polybutyl methacrylate, polyacrylic acid second
It is ester, polyvinyl alcohol, ethylene-acetate ethylene copolymer, polyvinyl acetate, polyurethane, melamino-formaldehyde, urea-formaldehyde, suitable
In anhydride maleique and its derivative and the copolymer of esters, polyacrylonitrile, makrolon, polysiloxanes, gelatin, starch extremely
Few one kind；Or the polymer is containing polyvinyl alcohol, polyethylene glycol oxide, Kynoar, Kynoar-hexafluoro third
Alkene copolymer, alkylated I oxide, polyvinylpyrrolidone, polyvinyl butyral, hydroxyethyl cellulose, methyl hydroxyl
Ethyl cellulose, sodium carboxymethylcellulose, cellulose acetate propionate, polyacrylamide, polymethyl methacrylate, poly- methyl-prop
Olefin(e) acid butyl ester, polyethyl acrylate, polyvinyl alcohol, ethylene-acetate ethylene copolymer, polyvinyl acetate, polyurethane, trimerization
Cyanamide formaldehyde, urea-formaldehyde, maleic anhydride and its derivative and the copolymer of esters, polyacrylonitrile, makrolon, poly- silicon
At least two copolymer in oxygen alkane.
The lithium salts of the present invention can be LiClO4、LiPF6Or Rf (Polyfluoroalkyl) replaces part F-, LiBF4Or Rf substitutions portion
Divide F-、LiAsF6Or Rf replaces part F-、LiSbF6Or Rf replaces part F-、LiB(C2O4)2、LiCF3SO3、LiCnF2n+1SO3(n
≥2)、LiC(CF3SO2)3、LiC(CnF2n+1SO2)3、LiCF3CO2、LiCnF2n+1CO2(n≥2)、LiC2F4(SO3)2、LiN
(FSO2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CnF2n+1SO2)2、LiN(RfOSO2)2At least one of.
Solid electrolyte layer can also contain inorganic filler, such as lithium metasilicate, lithium borate, lithium phosphate, lithium carbonate, aluminium oxide
Lithium, titanium oxide lithium, lanthana lithium, aluminum phosphate lithium, aluminum phosphate titanium lithium, aluminum phosphate germanium lithium, zirconic acid lanthanum lithium, silica, magnesia, oxygen
Change aluminium, calcium oxide, strontium oxide strontia, barium monoxide, titanium oxide, zirconium oxide, gallium oxide, tin oxide, calcium sulfate, strontium sulfate, barium sulfate, carbon
At least one of sour calcium, strontium carbonate, barium carbonate, aluminium hydroxide.The quality of inorganic filler accounts for solid electrolyte layer gross mass
0%~80%.Inorganic filler can improve the mechanical strength of solid electrolyte layer, and since inorganic filler can reduce polymer
Crystallinity, conductivity can be improved to a certain extent.
Steps are as follows for the preparation method of the negative current collector of the present invention：
Polymer, lithium salts and inorganic filler (when containing inorganic filler) are added in solvent and mixed, is made after stirring evenly
At solution or suspension；
Using porous current collector as collector matrix, solution obtained or suspension are coated on collector matrix,
Or collector matrix is immersed in solution or suspension obtained, after so that solution or suspension is attached on collector matrix
It takes out；
Collector matrix is dried, collector matrix surface is obtained and internal surface of hole is attached with solid electrolyte layer
Porous current collector.
When the solid electrolyte layer of collector matrix surface and internal surface of hole has two layers or two layers or more, adjacent two
The constituent of the solid electrolyte layer of layer can be not exactly the same.When solid electrolyte layer has two layers or two layers or more, weight
Multiple step 2 and step 3, you can obtain the negative current collector with multi-layer solid electrolyte layer.It is electrolysed when with multi-layer solid
When matter layer, the solid electrolyte layer not being in direct contact with porous current collector contains polymer, can contain lithium salts, can not also contain
Lithium salts can contain inorganic filler, can not also contain inorganic filler.
When the porous current collector of the present invention is used to prepare lithium battery as cathode pole piece, with conventional cathode pole piece, diaphragm
It is assembled into battery together, cathode pole piece is without filling any electrode active material at this time.
Below by specific embodiment, the present invention is further illustrated.Reagent, the material arrived used in following the description
Material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available, institute
The reagent being related to can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
By polyethylene glycol oxide and LiN (CF3SO2)2It is dissolved in acetonitrile, stirs evenly to form solution, wherein polyethylene glycol oxide
Quality account for 4%, the LiN (CF of solution gross mass3SO2)2Quality account for the 1.5% of solution gross mass；
The solution of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 24 hours.
Porous current collector is cut into growth 79mm, aluminium foil is cut growth by the rectangular pieces of width 45mm as cathode pole piece
The rectangle paillon of 95mm, width 40mm, and cobalt acid lithium is coated in the one side of aluminium foil, the area for coating cobalt acid lithium is less than cathode pole piece
Anode pole piece is made in area；Cathode pole piece, diaphragm, anode pole piece are stacked in order, after being encapsulated with aluminum plastic film, filling electrolysis
Liquid simultaneously seals, and monolithic battery is made.The electrolyte of the present embodiment is 1mol/L LiPF6EC/DEC/EMC solution, wherein EC/
The mass ratio of DEC/EMC is 1:1:1.
Embodiment 2
The present embodiment place different from embodiment 1 is：By polyethylene glycol oxide and LiN (CF3SO2)2It is dissolved in acetonitrile and stirring
Mix after being formed uniformly solution that (quality of polyethylene glycol oxide accounts for 4%, the LiN (CF of solution gross mass3SO2)2Quality to account for solution total
The 1.5% of quality), zirconic acid lanthanum lithium is added into solution, stirring forms suspension, wherein the quality of zirconic acid lanthanum lithium accounts for suspension
The 5% of gross mass；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 24 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 3
By polyacrylonitrile, LiN (CF3SO2)2、LiB(C2O4)2It is dissolved in acetonitrile, stirs evenly to form solution, wherein poly- third
The quality of alkene nitrile accounts for 5%, the LiN (CF of solution gross mass3SO2)2Quality account for 1%, the LiB (C of solution gross mass2O4)2Matter
Amount accounts for the 1% of solution gross mass, and lithium carbonate, lanthana lithium, barium sulfate are then added into solution, and stirring forms suspension,
In, the quality of lithium carbonate accounts for the 0.5% of suspension gross mass, and the quality of lanthana lithium accounts for the 0.5% of suspension gross mass, sulfuric acid
The quality of barium accounts for the 0.2% of suspension gross mass；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 24 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 4
By polyacrylonitrile, Kynoar, LiN (FSO2)2It is dissolved in NMP, stirs evenly to form solution, wherein polypropylene
The quality of nitrile accounts for the 5% of solution gross mass, and the quality of Kynoar accounts for 0.8%, the LiN (FSO of solution gross mass2)2Quality
The 2% of solution gross mass is accounted for, aluminum phosphate titanium lithium, aluminium oxide, silica are then added into solution, stirring forms suspension,
In, the quality of aluminum phosphate titanium lithium accounts for the 5% of suspension gross mass, and the quality of aluminium oxide accounts for the 0.2% of suspension gross mass, oxidation
The quality of silicon accounts for the 0.1% of suspension gross mass；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 48 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 5
By polyacrylonitrile, Kynoar-hexafluoropropylene copolymer, LiN (FSO2)2It is dissolved in NMP, stirs evenly to be formed
Solution, wherein the quality of polyacrylonitrile accounts for the 5% of solution gross mass, and that hexafluoropropylene copolymer accounts for solution to Kynoar-is total
0.5%, the LiN (FSO of quality2)2Quality account for the 2.5% of solution gross mass, zirconic acid lanthanum lithium, oxidation are then added into solution
Silicon, stirring form suspension, wherein the quality of zirconic acid lanthanum lithium accounts for the 10% of suspension gross mass, and the quality of silica accounts for suspended
The 0.1% of liquid gross mass；
Gained suspension is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 48 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 6
By polyethylene glycol oxide, polyacrylonitrile, sodium carboxymethylcellulose, LiN (FSO2)2It is dissolved in NMP, stirs evenly to be formed
Solution, wherein the quality of polyethylene glycol oxide accounts for the 3% of solution gross mass, and the quality of polyacrylonitrile accounts for the 2% of solution gross mass,
The quality of sodium carboxymethylcellulose accounts for 1%, the LiN (FSO of solution gross mass2)2Quality account for the 2.5% of solution gross mass, then
Aluminum phosphate titanium lithium, magnesia, barium monoxide are added into solution, stirring forms suspension, wherein the quality of aluminum phosphate titanium lithium accounts for outstanding
The 10% of turbid gross mass, the quality of magnesia account for the 0.5% of suspension gross mass, and the quality of barium monoxide accounts for suspension gross mass
0.5%；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the porous current collector with solid electrolyte layer after 48 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 7
By polyacrylonitrile, LiN (FSO2)2It is dissolved in NMP, stirs evenly to form solution, wherein the quality of polyacrylonitrile accounts for
5%, the LiN (FSO of solution gross mass2)2Quality account for the 2% of solution gross mass, be then added into solution aluminum phosphate titanium lithium,
Aluminium oxide, stirring form suspension, wherein the quality of aluminum phosphate titanium lithium accounts for the 8% of suspension gross mass, and the quality of aluminium oxide accounts for
The 0.5% of suspension gross mass；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the foam copper with solid electrolyte layer after 48 hours；
By polyethylene glycol oxide, LiN (CF3SO2)2It is dissolved in acetonitrile, stirs evenly to form solution, wherein polyethylene glycol oxide
Quality accounts for 5%, the LiN (FSO of solution gross mass2)2Quality account for the 2% of solution gross mass, be coated on it is dried have it is solid
On the foam copper of body electrolyte layer, then air drying obtains the porous current collector with two layers of solid electrolyte layer after 24 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Embodiment 8
By polyethylene glycol oxide, LiN (CF3SO2)2It is dissolved in acetonitrile, stirs evenly to form solution, wherein polyethylene glycol oxide
Quality accounts for 5%, the LiN (CF of solution gross mass3SO2)2Quality account for the 2% of solution gross mass, zirconic acid is then added into solution
Lanthanum lithium, magnesia, strontium oxide strontia, stirring form suspension, wherein the quality of zirconic acid lanthanum lithium accounts for the 8% of suspension gross mass, oxidation
The quality of magnesium accounts for the 0.2% of suspension gross mass, and the quality of magnesia accounts for the 0.1% of suspension gross mass；
The suspension of gained is coated on the foam copper that thickness is 1mm；
Air drying obtains the foam copper with solid electrolyte layer after 24 hours；
Polyacrylonitrile, Kynoar are dissolved in NMP, stir evenly to form solution, wherein the quality of polyacrylonitrile accounts for
The 3% of solution gross mass, the quality of Kynoar account for the 3% of solution gross mass, are coated on dried with solid electricity
On the foam copper for solving matter layer, then air drying obtains the porous current collector with two layers of solid electrolyte layer after 48 hours.
The rectangular pieces that porous current collector is cut to growth 79mm, width 45mm, as cathode pole piece, with diaphragm, positive pole
Piece stacks in order, after being encapsulated with aluminum plastic film, fills electrolyte and seals, monolithic battery is made.The anode pole piece of the present embodiment,
Diaphragm, electrolyte are same as Example 1.
Comparative example
The cathode pole piece of comparative example is the foam copper without any processing, and foam copper is cut growth 79mm, width 45mm
Rectangular pieces, stacked in order with diaphragm, anode pole piece, after being encapsulated with aluminum plastic film, filling electrolyte simultaneously seal, monolithic is made
Battery.Anode pole piece, diaphragm, the electrolyte of comparative example are same as Example 1.
Battery made from embodiment 1 to 8 and comparative example is subjected to cycle performance test, test method with reference to company standard,
Battery is subjected to charge and discharge cycles test under 0.2mA/cm2 current densities, test result is as follows shown in table.
By the test result of upper table it is found that porous current collector using the present invention is as cathode pole piece, the cycle of lithium battery
Performance be improved significantly.The present invention uses three-dimensional porous collector, and adheres to solid electricity in collector matrix surface and hole
Matter layer is solved, due to the lithium deposited when collector intrinsic silicon has big quantity space that can accommodate lithium battery charging, is deposited repeatedly in lithium
During abjection, the volume of collector itself remains unchanged, and reduces lithium metal volume in cyclic process and changes band repeatedly
The adverse effect come improves the cycle of lithium battery simultaneously because the presence of solid electrolyte layer, can inhibit the formation of Li dendrite
Performance.And due to not using lithium metal directly when battery makes, harsh environmental Kuznets Curves is not needed, lithium battery is reduced
Cost of manufacture.
The present invention uses three-dimensional porous collector directly as the cathode of lithium battery, can be according to the de- lithium amount of positive electrode
It estimates the volume of cathode deposition lithium metal, selects the three-dimensional porous collector with suitable porosity, suitable pore size；Or according to
The volume of collector calculates the space that lithium metal deposition can be accommodated in collector with porosimeter, and then determines positive electrode active materials
Usage amount so that space in three-dimensional porous afflux body opening is obtained fully while ensureing reserved enough lithium metal deposition spaces
It utilizes.
Such as：When use thickness is t (cm), porosity α, the foam copper that average pore size is r (μm) make porous current collector
When matrix, the pore volume total amount that the foam copper of unit area has is about t × α (cm3)；When foam copper surface and its internal surface of hole
When adhering to the solid electrolyte layer that thickness is δ (μm), the pore volume total amount which has is about t × α
×(1-δ/r)3(cm3).And the density of lithium metal is 0.534 (g/cm3), molal weight is 6.94 (g/mol), then theoretically should
The lithium metal amount that porous current collector unit area can deposit is 0.534 × t × α × (1- δ/r)3(g), i.e., the reason that lithium metal deposits
It is 0.534 × t × α × (1- δ/r) by the surface density upper limit3(g/cm2).If positive electrode active materials are LiCoO2, molal weight is
97.87 (g/mol) take off the lithium upper limit and are calculated by 50%, and for monolithic battery, a piece of porous current collector corresponds to a positive plate, then
LiCoO in positive plate2The theoretical surface density upper limit should be 15.06 × t × α × (1- δ/r)3(g/cm2)；For laminated batteries, one
Piece porous current collector is shared by both sides anode, then should be 7.53 × t × α × (1- per the theoretical surface density upper limit of side positive plate
δ/r)3(g/cm2), the usage amount of positive electrode active materials thus can be determined with porosity according to the volume of collector, to make full use of
Space in the hole of porous current collector.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (14)
1. porous current collector includes the collector matrix with pore space structure, it is characterised in that：The collector matrix surface with
And internal surface of hole is attached with solid electrolyte layer, the solid electrolyte layer is at least one layer.
2. porous current collector as described in claim 1, it is characterised in that：The solid electrolyte layer contains polymer and lithium
Salt.
3. porous current collector as claimed in claim 2, it is characterised in that：The polymer be polyvinyl alcohol, polyethylene glycol oxide,
Kynoar, Kynoar-hexafluoropropylene copolymer, alkylated I oxide, polyvinylpyrrolidone, poly- second
Enol butyral, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, cellulose acetate propionate, polypropylene
Amide, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate are total
Polymers, polyvinyl acetate, polyurethane, melamino-formaldehyde, urea-formaldehyde, maleic anhydride and its derivative and esters
At least one of copolymer, polyacrylonitrile, makrolon, polysiloxanes, gelatin, starch；Or the polymer be containing
Polyvinyl alcohol, polyethylene glycol oxide, Kynoar, Kynoar-hexafluoropropylene copolymer, alkylated I oxide,
Polyvinylpyrrolidone, polyvinyl butyral, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, vinegar
Sour cellulose propionate, polyacrylamide, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyethylene
Alcohol, ethylene-acetate ethylene copolymer, polyvinyl acetate, polyurethane, melamino-formaldehyde, urea-formaldehyde, maleic acid
At least two copolymer in acid anhydride and its derivative and the copolymer of esters, polyacrylonitrile, makrolon, polysiloxanes.
4. porous current collector as claimed in claim 2 or claim 3, it is characterised in that：The lithium salts is LiClO4、LiPF6Or Rf substitutions
Part F-, LiBF4Or Rf replaces part F-、LiAsF6Or Rf replaces part F-、LiSbF6Or Rf replaces part F-、LiB(C2O4)2、
LiCF3SO3、LiCnF2n+1SO3(n≥2)、LiC(CF3SO2)3、LiC(CnF2n+1SO2)3、LiCF3CO2、LiCnF2n+1CO2(n≥2)、
LiC2F4(SO3)2、LiN(FSO2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CnF2n+1SO2)2、LiN(RfOSO2)2In
It is at least one.
5. porous current collector as claimed in claim 2 or claim 3, it is characterised in that：The solid electrolyte layer contains inorganic filler,
The quality of the inorganic filler accounts for the 0%~80% of solid electrolyte layer gross mass.
6. porous current collector as claimed in claim 5, it is characterised in that：The inorganic filler is lithium metasilicate, lithium borate, phosphoric acid
Lithium, lithium carbonate, aluminium oxide lithium, titanium oxide lithium, lanthana lithium, aluminum phosphate lithium, aluminum phosphate titanium lithium, aluminum phosphate germanium lithium, zirconic acid lanthanum lithium,
Silica, magnesia, aluminium oxide, calcium oxide, strontium oxide strontia, barium monoxide, titanium oxide, zirconium oxide, gallium oxide, tin oxide, calcium sulfate,
At least one of strontium sulfate, barium sulfate, calcium carbonate, strontium carbonate, barium carbonate, aluminium hydroxide.
7. porous current collector as described in claim 1, it is characterised in that：The thickness of the collector matrix is 1 μm~2000 μ
m。
8. porous current collector as described in claim 1, it is characterised in that：The thickness of the solid electrolyte layer be 0.01 μm~
30μm。
9. the preparation method of the porous current collector as described in claims 1 or 2 or 3 or 4 or 7 or 8, which is characterized in that including with
Lower step：
Polymer, lithium salts are added in solvent and are mixed, solution is made after stirring evenly；
Solution obtained is coated on collector matrix, or collector matrix is put into solution obtained after immersion and is taken
Go out；
Collector matrix is dried, collector matrix surface is obtained and internal surface of hole is attached with the porous of solid electrolyte layer
Collector.
10. such as the preparation method of porous current collector described in claim 5 or 6, which is characterized in that include the following steps：
Polymer, lithium salts are added in solvent and carry out being mixed and made into solution, inorganic filler is added into solution, stirs evenly and is made
Suspension；
Suspension obtained is coated on collector matrix, or collector matrix is put into suspension obtained after immersion
It takes out；
Collector matrix is dried, collector matrix surface is obtained and internal surface of hole is attached with the porous of solid electrolyte layer
Collector.
11. the preparation method of the porous current collector as described in claim 9 or 10, it is characterised in that：The quality of the polymer
The 4~6% of solution gross mass are accounted for, the quality of the lithium salts accounts for the 1.5~2.5% of solution gross mass.
12. the preparation method of porous current collector as claimed in claim 10, it is characterised in that：The quality of the polymer accounts for molten
The 4~6% of liquid gross mass, the quality of the lithium salts account for the 1.5~2.5% of solution gross mass, and the quality of the inorganic filler accounts for
The 0.9~11% of suspension gross mass.
13. the preparation method of the porous current collector as described in claim 9 or 10, it is characterised in that：The collector matrix table
When the solid electrolyte layer of face and internal surface of hole has two layers or two layers or more, the composition of the solid electrolyte layer of adjacent two layers
Ingredient is not exactly the same, and the solid electrolyte layer not being in direct contact with collector matrix contains polymer, or contains polymer
And lithium salts and/or inorganic filler.
14. lithium battery, including anode pole piece, cathode pole piece and diaphragm, it is characterised in that：The cathode pole piece is using such as right
It is required that porous current collector made from the preparation method of 9 to 13 any one of them porous current collectors, do not filled out on the cathode pole piece
Fill electrode active material.
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