CN108550808A - A kind of composition metal cathode of lithium and preparation method thereof - Google Patents
A kind of composition metal cathode of lithium and preparation method thereof Download PDFInfo
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- CN108550808A CN108550808A CN201810311716.1A CN201810311716A CN108550808A CN 108550808 A CN108550808 A CN 108550808A CN 201810311716 A CN201810311716 A CN 201810311716A CN 108550808 A CN108550808 A CN 108550808A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 140
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000010276 construction Methods 0.000 claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000003780 insertion Methods 0.000 claims description 5
- 230000037431 insertion Effects 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 19
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- 238000009825 accumulation Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Include the primary network station structure set up by polymer the present invention provides a kind of composition metal cathode of lithium；Nano-scale carbon material is filled into the two grade network structure constituted in primary network station structure；Lithium metal is filled into the three-level composite construction constituted in two grade network structure.The two grade network structure of carbon material filling is obtained using accumulation ply rolling method first, then lithium metal is embedded in the two grade network structure of carbon material filling and obtains composition metal cathode of lithium by accumulating ply rolling method, electro-deposition lithium or evaporation plating lithium.The structure cathode can improve lithium deposition morphology, solve the problems, such as lithium dendrite growth, to improve cycle performance and the safety of battery.
Description
Technical field
The invention belongs to field of lithium ion secondary, more particularly to a kind of composition metal cathode of lithium and preparation method thereof.
Background technology
Lithium rechargeable battery is to move externally to provide electric energy between a positive electrode and a negative electrode using lithium ion.Improve lithium from
The ratio energy of sub- secondary cell is the main direction of development of current lithium rechargeable battery development.One of them effective method
It is to use lithium metal as cathode.This is because Unit Weight or the lithium metal of volume move to the discharge process of anode from cathode
In, most energy can be released, i.e. lithium metal is that have highest weight or volume than the negative electrode active material of energy.However
Lithium metal can grow Li dendrite during charge and discharge cycles on surface, lead to cathode of lithium dusting, increase the internal resistance of cell, reduce electricity
Tankage influences the service life.More seriously, Li dendrite can constantly be grown, and can be pierced through diaphragm, be in contact with anode, in generation
Portion's short circuit, brings serious safety problem.Therefore, solve the problems, such as that the growth of Li dendrite is cathode of lithium functionization and must solve.
In order to inhibit the growth of Li dendrite, scientist and engineering staff to be made that many researchs and effort.These work master
Concentrate on the following aspects.(1) according to document Energy Environ.Sci.2014,7,513 and Adv.Sci.2016,
3,1500213 and patent CN103531839 is disclosed, by the way that additive, regulation and control lithium anode surface are added in the electrolytic solution
SEI ingredients and pattern, form stable SEI dendrite inhibitions growth.(2) construction artificial SEI in situ, protection lithium metal are negative
Pole.(3) polymer dielectric or all solid state electrolyte, blocking Li dendrite is used to generate.However these method and measures have very
Big deficiency.During lithium an- ode cycle charge-discharge, prodigious volume change can be undergone, therefore either electrolyte adds
Add agent or artificial SEI in situ, all not enough intensity and toughness, the volume change that can bear lithium metal cycle is not broken
It is broken.Especially as the current density increases, even more so.According to theoretical calculation, only when electrolyte strength is more than 6Gpa, ability
Blocking Li dendrite completely punctures, however existing polymer dielectric does not all reach such high intensity.In addition Li dendrite can be along
The crystal boundary of all solid state electrolyte is diffused, to which short circuit occur across all solid state electrolyte.Therefore polymer dielectric and complete
Solid electrolyte can not solve the problems, such as lithium dendrite growth.
In addition to from SEI and the solution of electrolyte direction, also a few thing is conceived to the structure optimization of lithium anode.Patent
CN105845891A discloses a kind of double-level-metal cathode of lithium structure.There is coating in metallic lithium surface, coating is by carbon materials
One or several kinds of compositions of material, polymer material, glass.Coating influences electrochemical environment when lithium deposition, to inhibit
The growth of Li dendrite.However according to inventor the study found that overburden cover thicker must can just be enough to change the electricity of lithium deposition
Chemical environment achievees the effect that dendrite inhibition.Coating can reduce the energy density of battery, increase the internal resistance of battery, influence electricity
Pond performance.In addition the invention can not realize the double-layer structure by mass production processes.Document NATURE NANOTECHNOLOGY
VOL 11,2016,7 proposes a kind of new resolving ideas.Multilayer graphene oxide is immersed in liquid lithium, is made by capillary
With the multilayered structure of formation graphene sheet layer/lithium metal.The lithium anode of this structure is during cycle charge-discharge, tool
There is good electro-chemical activity, it being capable of dendrite inhibition growth.However the complex process, required graphene oxide sheet still cannot
Continuous production can only use the method small area filtered to make.In particular for the liquid lithium for using melting, can only be protected in Ar gas
It is operated under shield.Generally this method does not have the meaning and value of amplification and practical application.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which it is negative to provide a kind of lithium rechargeable battery composite metal lithium
Pole avoids electrode dusting and battery internal short-circuit in battery charging and discharging cyclic process.
The technical solution adopted by the present invention is：A kind of lithium anode with three-level composite construction, the compound gold are provided
Belonging to cathode of lithium includes：The primary network station structure set up by polymer；Nano-scale carbon material is filled into primary network station structure and constitutes
Two grade network structure；Lithium metal is filled into the three-level composite construction constituted in two grade network structure.
Pore diameter range in the composition metal cathode of lithium primary network station structure is 0.1 μm~1mm, porosity is 10%~
99%；Pore diameter range in two grade network structure is 10nm~1mm, and porosity is 9%~98%；Hole in three-level composite construction
Diameter ranging from 0nm~0.1mm, porosity are 0%~50%.
The preferred three-level composite construction of the composition metal cathode of lithium is：Aperture in primary network station structure is 0.2 μm~2 μ
M, porosity are 60%~95%；Aperture in two grade network structure is 0.05 μm~1 μm, and porosity is 50%~85%；Three
Aperture in grade composite construction is 0nm~100nm, and porosity is 0%~5%.
The thickness of the composition metal cathode of lithium is 0.05 μm~1mm.
Polymer described in the composition metal cathode of lithium is polytetrafluoroethylene (PTFE) (PTFE), Kynoar, polyimides,
Polyacrylonitrile, polyaniline, polylactic acid is one or more in cellulose acetate and polylactide glycolate copolymer, and preferably poly- four
Vinyl fluoride, mass content are 2%~20%.
Nano-scale carbon material described in the composition metal cathode of lithium is natural graphite, artificial graphite, modified graphite, graphite
Change carbon, activated carbon, hard carbon, soft carbon is one or more in graphene, and mass content is 15%~70%.
The mass content of lithium metal described in the composition metal cathode of lithium is 20%~80%.
The present invention also provides the preparation methods of composition metal cathode of lithium, specially：Using the caking property of polymer, use
Metal rolled method rolling, it is 10%~50% to push deflection, obtains the three-dimensional network polymer by once rolling；By carbon
Material is laid in three-dimensional network polymer surfaces, is then rolled, and pushes deflection 20%~50%, carbon is filled into three dimensional network
In network structure, the secondary structure filled by carbon is obtained；Lithium metal is laid in secondary structure surface, is then rolled, is pushed
Deflection 20%~50%, a part of lithium metal are embedded in carbon material, and a part of lithium metal is filled into the gap of three-dimensional structure,
First of composition metal cathode of lithium is obtained, above-mentioned composition metal cathode of lithium is cut out, is overlapped, is rolled, 3~20 times repeatedly,
Obtain the uniform composition metal cathode of lithium of microstructure.
Further, the preparation method of the composition metal cathode of lithium is：Lithium metal is embedded in by carbon materials using electro-deposition lithium
Expect the two grade network structure of filling or lithium is plated by the two grade network structure of lithium metal insertion carbon material filling using evaporation.
The present inventor is by consulting literatures data and carries out related experiment, is formed to Li dendrite and growth is studied.
In charging process, in negative terminal surface electrochemical reaction can occur for lithium ion, when the electrochemical potentials on surface are less than Li+/ Li electricity
Position occurs negative terminal surface and analyses lithium.The electrochemical potentials of negative terminal surface are affected by various factors, such as Li+Concentration, cathode
Average potential and electrode surface microscopic appearance etc..Wherein electrode surface pattern influences lithium deposition particularly evident：In electrode
Surface curvature radius small region such as Defect Edge, protrusion etc., charge is more easy to be enriched with, its current potential is caused to be less than other regions, past
Occur analysing lithium toward preferential；The lithium metal of deposition aggravates the inconsistent of surface topography again, leads to lithium dendrite growth.
The prior art be all chemically solve the above problems with film fabrication techniques, but chemical method there are complex process,
The not low problem of easy-regulating, degree of being practical improves the limitation of the cycle performance of battery；There are costs for film fabrication techniques
It is high, harsh to environmental requirement, practical difficult problem.It all can not thoroughly solve lithium dusting and Li dendrite existing for cathode of lithium
Problem.
Advantageous effect：
Composite metal lithium negative pole structure provided by the invention, the structure cathode can improve lithium deposition morphology, solve Li dendrite
Growth question, to improve cycle performance and the safety of battery：First, micrograde polymer skeleton have high stability and
ElectrochemicaUy inert does not interfere with the performance of battery, also, the carbon and lithium that are distributed in the network architecture may insure that the structure has
Good electronic conductance, it is ensured that normal sedimentation/dissolution of lithium；Secondly, lithium is evenly distributed in the network architecture, in lithium process in leaching
Middle lithium carbon-coating provides portion capacity as lithium source；Lithium carbon-coating can balance negative terminal surface current potential, dendrite inhibition growth when lithium deposits；
Third, the micrograde polymer skeleton in the complex lithium negative pole structure can provide space for lithium deposition/dissolution, alleviate negative electrode volume
Variation improves structural stability.
Description of the drawings
Fig. 1 is composite metal lithium negative pole structure schematic diagram of the present invention；
Fig. 2 is the cycle figure that composition metal cathode of lithium using the present invention makes Symmetrical cells；
Fig. 3 is the cycle result figure that Symmetrical cells are made of conventional lithium an- ode；
Specific implementation mode
Embodiment 1
Polymer content is 2% in composition metal cathode of lithium, and nano-scale carbon material content is 25%, and the content of lithium metal is
73%.
Composition metal cathode of lithium is obtained using accumulation ply rolling method, specific method is：Using the caking property of polymer P TFE, adopt
It is rolled with metal rolled method, it is 10%~50% to push deflection, obtains the three-dimensional network polymer by once rolling；It will
Carbon material is laid in three-dimensional network polymer surfaces, is then rolled, and pushes deflection 20%~50%, carbon is filled into three-dimensional
In network structure, the secondary structure filled by carbon is obtained；Lithium metal is laid in secondary structure surface, is then rolled, under
Compressive strain amount 20%~50%, a part of lithium metal are embedded in carbon material, and a part of lithium metal is filled into the gap of three-dimensional structure
In, obtain first of composition metal cathode of lithium.Above-mentioned composition metal cathode of lithium is cut out, is overlapped, is rolled, repeatedly 3~20
It is secondary, obtain the uniform composition metal cathode of lithium of microstructure.For the technology according to polymer, nano-scale carbon and lithium metal are yielding
Feature, the significant shear power generated in severe plastic deformation using polymer are formed skeleton, and carbon material and lithium metal are disperseed
Wherein.Form the three-level composite construction composite metal lithium being combined with micrograde polymer/nano-scale carbon/lithium metal
Cathode has unique heterogeneous microstructure and excellent mechanical performance.
Fig. 2 and Fig. 3 shows that the overpotential of composition metal cathode of lithium using the present invention is obviously lower than conventional cathode of lithium, follows
Ring stability is preferable.
Embodiment 2
Polymer content is 10% in composition metal cathode of lithium, and nano-scale carbon material content is 50%, the content of lithium metal
It is 40%.
Composition metal cathode of lithium is obtained using accumulation ply rolling method, specific method is the same as embodiment 1.
Embodiment 3
Polymer content is 20% in composition metal cathode of lithium, and nano-scale carbon material content is 30%, the content of lithium metal
It is 50%.
Composition metal cathode of lithium is obtained using accumulation ply rolling method, specific method is the same as embodiment 1.
Embodiment 4
Obtaining the specific method of composition metal cathode of lithium is：Using the caking property of polymer P TFE, using metal rolled side
Method rolls, and it is 10%~50% to push deflection, obtains the three-dimensional network polymer by once rolling；Carbon material is laid in
Three-dimensional network polymer surfaces, are then rolled, and deflection 20%~50% is pushed, and carbon is filled into three-dimensional net structure,
Obtain the secondary structure filled by carbon；Then use electro-deposition lithium by the two grade network structure of lithium metal insertion carbon material filling
In, three-level composite construction composition metal cathode of lithium is made.
Embodiment 5
Obtaining the specific method of composition metal cathode of lithium is：Using the caking property of polymer P TFE, using metal rolled side
Method rolls, and it is 10%~50% to push deflection, obtains the three-dimensional network polymer by once rolling；Carbon material is laid in
Three-dimensional network polymer surfaces, are then rolled, and deflection 20%~50% is pushed, and carbon is filled into three-dimensional net structure,
Obtain the secondary structure filled by carbon；Then the two grade network structure filled lithium metal insertion carbon material using evaporation plating lithium
In, three-level composite construction composition metal cathode of lithium is made.
Comparative example
106784635 A of patent CN provide a kind of preparation method of the compound cathode of lithium of solid state battery, are inculcated by heat
Method either electrodeposition process lithium metal is deposited on it is compound to be prepared in three-dimensional carbon material or foam porous material void
Cathode of lithium, the application of wherein three-dimensional framework are played and are pre-stored space and circulating battery process that lithium provides abundance in preparation process
Middle reception lithium metal provides carrier, plays circulating battery and inhibits lithium dendrite growth, stabilized electrodes volume change, cycle in the process
Stability is good and advantage with long service life.
The structure of composition metal cathode of lithium uses polymer for three-dimensional framework in patent of the present invention, compares the intensity of carbon skeleton
It is more preferable with toughness, thus structure is more stable；And accomplished in many ways may be used, machinability is strong；And tune can be passed through
The component of whole polymer, carbon and lithium metal carrys out the structure of controlled material, and structure has variability, controllability；What is more important,
Since polymer backbone is more more stable than carbon skeleton, preferably stabilized electrodes volume change, good cycling stability the longevity can be used
It orders longer.
The above is the preferred embodiment of the present invention, and the interest field of the present invention cannot be defined with this.It should be pointed out that
For those skilled in the art, technical scheme of the present invention is modified or replaced equivalently, not
It is detached from protection scope of the present invention.
Claims (9)
1. a kind of composition metal cathode of lithium, it is characterised in that：The cathode includes：The primary network station structure set up by polymer；
Nano-scale carbon material is filled into the two grade network structure constituted in primary network station structure；Lithium metal is filled into two grade network structure
The three-level composite construction of composition forms composition metal cathode of lithium.
2. composition metal cathode of lithium according to claim 1, it is characterised in that：Aperture in the primary network station structure is
0.1 μm~1mm, porosity is 10%~99%；Aperture in two grade network structure is 10nm~1mm, porosity is 9%~
98%；Aperture in three-level composite construction is 0nm~0.1mm, and porosity is 0%~50%.
3. composition metal cathode of lithium according to claim 2, it is characterised in that：Aperture in the primary network station structure is
0.2 μm~2 μm, porosity is 60%~95%；Aperture in two grade network structure is 0.05 μm~1 μm, porosity 50%
~85%；Aperture in three-level composite construction is 0nm~100nm, and porosity is 0%~5%.
4. composition metal cathode of lithium according to claim 1, it is characterised in that：The thickness of the composition metal cathode of lithium
For 0.05 μm~1mm.
5. composition metal cathode of lithium according to claim 1, it is characterised in that：The polymer is polytetrafluoroethylene (PTFE),
Kynoar, polyimides, polyacrylonitrile, polyaniline, polylactic acid, in cellulose acetate and polylactide glycolate copolymer
One or more, content is 2%~20%.
6. composition metal cathode of lithium according to claim 1, it is characterised in that：The nano-scale carbon material is natural stone
Ink, artificial graphite, modified graphite, graphitized carbon, activated carbon, hard carbon, soft carbon, one or more in graphene, content is
15%~70%.
7. composition metal cathode of lithium according to claim 1, it is characterised in that：The content of the lithium metal be 20%~
80%.
8. a kind of preparation method of composition metal cathode of lithium according to claim 1, it is characterised in that：The preparation method
For：Polymer is rolled using metal rolled method, it is 10%~50% to push deflection, obtains the three dimensional network by once rolling
Network polymer；Carbon material is laid in three-dimensional network polymer surfaces, is rolled, pushes deflection 20%~50%, carbon is filled out
It is charged in three-dimensional net structure, obtains the secondary structure filled by carbon；Lithium metal is laid in secondary structure surface, is then carried out
Rolling pushes deflection 20%~50%, and a part of lithium metal is embedded in carbon material, and a part of lithium metal is filled into three-dimensional structure
Gap in, obtain first of composition metal cathode of lithium, above-mentioned composition metal cathode of lithium is cut out, is overlapped, roll, repeatedly
3~20 times, obtain the uniform composition metal cathode of lithium of microstructure.
9. the preparation method of composition metal cathode of lithium according to claim 8, it is characterised in that：The composite metal lithium is negative
The preparation method of pole is：Using electro-deposition lithium by the two grade network structure of lithium metal insertion carbon material filling or using evaporation plating lithium
By the two grade network structure of lithium metal insertion carbon material filling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810311716.1A CN108550808B (en) | 2018-04-09 | 2018-04-09 | Composite metal lithium cathode and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810311716.1A CN108550808B (en) | 2018-04-09 | 2018-04-09 | Composite metal lithium cathode and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108550808A true CN108550808A (en) | 2018-09-18 |
| CN108550808B CN108550808B (en) | 2021-04-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411694A (en) * | 2018-10-22 | 2019-03-01 | 天齐锂业（江苏）有限公司 | A kind of lithium metal composite negative pole and the preparation method and application thereof |
| CN110085804A (en) * | 2019-05-16 | 2019-08-02 | 珠海冠宇电池有限公司 | A kind of Ultralight composite negative pole and the lithium ion battery containing the cathode |
| CN110660969A (en) * | 2019-09-20 | 2020-01-07 | 清华大学深圳国际研究生院 | Metallic lithium cathode and preparation method thereof |
| CN111916682A (en) * | 2020-09-17 | 2020-11-10 | 天目湖先进储能技术研究院有限公司 | Composite metal lithium cathode, preparation method thereof and lithium battery |
| CN114300654A (en) * | 2021-12-31 | 2022-04-08 | 四川启睿克科技有限公司 | Uniformly-distributed three-dimensional lithium alloy cathode and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101459238A (en) * | 2008-12-23 | 2009-06-17 | 大连海事大学 | Manufacturing method for high capacity composite electrode of lithium ionic cell |
| CN102354759A (en) * | 2011-11-04 | 2012-02-15 | 上海空间电源研究所 | Lithium negative pole, preparation method thereof and battery comprising lithium negative pole |
| CN102610831A (en) * | 2012-03-26 | 2012-07-25 | 龙能科技（苏州）有限公司 | Electrode of lithium ion battery and preparation method thereof |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105129763A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of three-dimensional graphene/mesoporous carbon sphere composite material |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN106876662A (en) * | 2017-01-23 | 2017-06-20 | 浙江大学 | A kind of metal electrode with three-dimensional structure |
| CN106935905A (en) * | 2017-03-01 | 2017-07-07 | 复旦大学 | A kind of fibrous lithium-air battery of high-temperature stable and preparation method thereof |
| CN107611391A (en) * | 2017-09-05 | 2018-01-19 | 珠海格力电器股份有限公司 | A kind of lithium metal secondary battery negative pole and preparation method thereof |
| CN107706350A (en) * | 2017-10-16 | 2018-02-16 | 四川华昆能源有限责任公司 | The electrode structure of three-dimensional lithium anode and its corresponding lithium-sulfur cell preparation method |
-
2018
- 2018-04-09 CN CN201810311716.1A patent/CN108550808B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101459238A (en) * | 2008-12-23 | 2009-06-17 | 大连海事大学 | Manufacturing method for high capacity composite electrode of lithium ionic cell |
| CN102354759A (en) * | 2011-11-04 | 2012-02-15 | 上海空间电源研究所 | Lithium negative pole, preparation method thereof and battery comprising lithium negative pole |
| CN102610831A (en) * | 2012-03-26 | 2012-07-25 | 龙能科技（苏州）有限公司 | Electrode of lithium ion battery and preparation method thereof |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105129763A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of three-dimensional graphene/mesoporous carbon sphere composite material |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN106876662A (en) * | 2017-01-23 | 2017-06-20 | 浙江大学 | A kind of metal electrode with three-dimensional structure |
| CN106935905A (en) * | 2017-03-01 | 2017-07-07 | 复旦大学 | A kind of fibrous lithium-air battery of high-temperature stable and preparation method thereof |
| CN107611391A (en) * | 2017-09-05 | 2018-01-19 | 珠海格力电器股份有限公司 | A kind of lithium metal secondary battery negative pole and preparation method thereof |
| CN107706350A (en) * | 2017-10-16 | 2018-02-16 | 四川华昆能源有限责任公司 | The electrode structure of three-dimensional lithium anode and its corresponding lithium-sulfur cell preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411694A (en) * | 2018-10-22 | 2019-03-01 | 天齐锂业（江苏）有限公司 | A kind of lithium metal composite negative pole and the preparation method and application thereof |
| CN110085804A (en) * | 2019-05-16 | 2019-08-02 | 珠海冠宇电池有限公司 | A kind of Ultralight composite negative pole and the lithium ion battery containing the cathode |
| CN110660969A (en) * | 2019-09-20 | 2020-01-07 | 清华大学深圳国际研究生院 | Metallic lithium cathode and preparation method thereof |
| CN111916682A (en) * | 2020-09-17 | 2020-11-10 | 天目湖先进储能技术研究院有限公司 | Composite metal lithium cathode, preparation method thereof and lithium battery |
| CN114300654A (en) * | 2021-12-31 | 2022-04-08 | 四川启睿克科技有限公司 | Uniformly-distributed three-dimensional lithium alloy cathode and preparation method thereof |
| CN114300654B (en) * | 2021-12-31 | 2023-06-09 | 四川启睿克科技有限公司 | Uniformly-distributed three-dimensional lithium alloy negative electrode and preparation method thereof |
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