CN110061190A - Liquid metal-based self-healing lithium battery cathode, preparation method and lithium ion battery - Google Patents
Liquid metal-based self-healing lithium battery cathode, preparation method and lithium ion battery Download PDFInfo
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- CN110061190A CN110061190A CN201810544833.2A CN201810544833A CN110061190A CN 110061190 A CN110061190 A CN 110061190A CN 201810544833 A CN201810544833 A CN 201810544833A CN 110061190 A CN110061190 A CN 110061190A
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- liquid metal
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- healing
- lithium cell
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 131
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 68
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims description 37
- 239000005543 nano-size silicon particle Substances 0.000 claims description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052733 gallium Inorganic materials 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 235000013339 cereals Nutrition 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000002210 silicon-based material Substances 0.000 abstract description 12
- 210000004027 cell Anatomy 0.000 description 26
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 12
- 239000011856 silicon-based particle Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
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- 230000009471 action Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/626—Metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and particularly provides a liquid metal-based self-healing lithium battery cathode, a preparation method and a lithium ion battery. The liquid metal-based self-healing lithium battery negative electrode comprises a negative electrode current collector and a negative electrode material attached to the surface of the negative electrode current collector, wherein the negative electrode material comprises a composite material of liquid metal nanoparticles and silicon and a binder; the composite material of the liquid metal nanoparticles and the silicon comprises the following components in percentage by mass: binder (9-90): 1; in the composite material of the liquid metal nanoparticles and the silicon, the mass ratio of the liquid metal nanoparticles to the silicon is 1: (1-5). When the cathode is assembled into a lithium ion battery, the liquid metal nanoparticles can self-repair the silicon material, so that the lithium ion battery has an ultra-long cycle characteristic, can realize quick charge and can perform high-rate discharge.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of liquid metal matrix self-healing lithium cell negative pole and system
Preparation Method and lithium ion battery.
Background technique
With the demand for development to technologies such as energy storage device higher energy density, long circulating and ultrafast charge and discharge, exploitation is more
Outstanding electrode material of new generation is particularly important.Its theoretical specific capacity of business lithium battery uses at present graphite cathode material
Only 372mAh/g, it is difficult to meet the application demand of novel high-energy metric density lithium battery.Although lithium an- ode has very high
Specific capacity (3860mAh/g), but Li dendrite easy to form during circulating battery, service life are not grown, while being easy to cause peace
Full problem.In comparison, silicium cathode has higher theoretical specific capacity (4212mAh/g (Li4.4Si)), and discharge platform compared with
It is low, it is not easy that Li dendrite is precipitated, security performance is more preferable.However, the practical application of silicium cathode still has huge challenge, major embodiment
In the following aspects: 1) charge and discharge cycles during, the insertion of lithium ion and abjection can make material volume occur 300% with
On variation, make material gradually dusting, eventually lead to electrode active material and collector and be detached from, destroy conductive network, lead to electricity
Pond cycle performance reduces.2) silicon self-conductance rate is lower.3) bulk effect makes silicon be difficult to form stable consolidate in the electrolytic solution
Body electrolyte interface (SEI) film, reduces coulombic efficiency while exacerbating the decaying of capacity.
Summary of the invention
Cause SEI film unstable for current silicon substrate lithium ion battery volume expansion in charge and discharge process is excessive, finally
Lead to problems such as battery cycle life short, the present invention provides a kind of liquid metal matrix self-healing lithium cell negative pole and preparation method.
And liquid metal matrix self-healing lithium cell negative pole the answering in lithium ion battery obtained by above-mentioned preparation method
With.
For achieving the above object, technical scheme is as follows:
A kind of liquid metal matrix self-healing lithium cell negative pole, including negative current collector and it is attached to the negative current collector surface
Negative electrode material, the negative electrode material includes the composite material of liquid metal nano particle and silicon, binder；
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1；
Wherein, in the composite material of the liquid metal nano particle and silicon, the quality of liquid metal nano particle and silicon
Than for 1:(1~5).
Correspondingly, a kind of preparation method of liquid metal matrix self-healing lithium cell negative pole, at least includes the following steps:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, is obtained liquid metal and is received
The composite material of rice grain and silicon；
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, is made
The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing, obtain liquid metal matrix by slurry
Self-healing lithium cell negative pole.
And a kind of lithium ion battery, including anode, cathode, diaphragm, electrolyte and battery case, the cathode are as above
The liquid metal matrix self-healing lithium cell negative pole or the cathode are using liquid metal matrix self-healing lithium electricity as described above
The preparation method of cathode is prepared.
The beneficial effect of liquid metal matrix self-healing lithium cell negative pole of the present invention is:
Compared with the existing technology, liquid metal matrix self-healing lithium cell negative pole of the invention does not need to add additional conduction
Agent, but directly improve the content of silicon materials using liquid metal nano particle as self-repair material and conductive agent, used
When on lithium ion battery, there is good interfacial contact and ultralow resistivity, liquid metal nano particle can be to silicon
Material carries out self-regeneration, to have overlength cycle characteristics, and quick charge may be implemented, can carry out high-multiplying power discharge.
The preparation method of liquid metal matrix self-healing lithium cell negative pole provided by the invention, preparation process is few, high production efficiency,
Production cost is low, and seamless connection, easily realization industrialization can be realized with present industry line.
Lithium ion battery provided by the invention can be effective since cathode uses liquid metals base self-healing lithium cell negative pole
Ground improves the coulombic efficiency of lithium ion battery, and carries out selfreparing to silicium cathode material by liquid metal, avoids SEI film
It is unstable, it is contacted in conjunction with liquid metal with the good interface of silicon materials and the super-low resistivity of liquid metal, realizes lithium ion
The high power charging-discharging and long circulation life of battery.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the SEM figure that liquid metal nano particle of the present invention amplifies 10000 times；
Fig. 2 is the cathode amplification 5000 that 1 liquid metal nano particle of the embodiment of the present invention and silicon nanoparticle are mixed to get
SEM figure again；
Fig. 3 is the cathode amplification 10000 that 2 liquid metal nano particle of the embodiment of the present invention and micron silicon particle are mixed to get
SEM figure again；
Fig. 4 is that the cathode that 3 liquid metal nano particle of the embodiment of the present invention and silicon carbide particles are mixed to get amplifies 500 times
SEM figure；
Fig. 5 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of cycle performance test；
Fig. 6 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of different multiplying test；
Fig. 7 is that the cathode of the embodiment of the present invention 1 is assembled into lithium ion battery and carries out the curve of coulombic efficiency test；
Fig. 8 is the operation principle schematic diagram of liquid metal nano particle of the present invention and silicon materials interaction.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
Present example provides a kind of liquid metal matrix self-healing lithium cell negative pole, including negative current collector and is attached to described
The negative electrode material on negative current collector surface, the negative electrode material include the composite material of liquid metal nano particle and silicon, bonding
Agent；
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1；
Wherein, in the composite material of the liquid metal nano particle and silicon, the quality of liquid metal nano particle and silicon
Than for 1:(1~5).
Preparation method technical solution of the invention is further explained in detail below.
The above-mentioned negative current collector of the present invention can be copper foil.
Preferably, the liquid metal nano particle is the mixture of gallium, indium, tin, and the mass ratio of the gallium, indium, tin
For (6~9): (1~3): 1.Three kinds of metals of gallium indium tin have good interaction under the mixed proportion, with silicon materials, and
And the volume expansion of silicon particle is utilized in chemical reaction process, cause mechanical stress to squeeze liquid metal-to-metal adhesive capsule crust, so that
Silicon destroys liquid metal capsule autoxidation shell in initial lithiation, the excessive disperse of liquid metal is caused, to significantly increase
Connectivity in electric conductivity and electrode microstructure, specific action principle are as shown in Figure 8.Have by liquid metal Nano capsule
Self-healing properties and high capacity silicon materials between interaction so that obtain liquid metal matrix self-healing lithium cell negative pole exist
When lithium ion battery is made in lithium ion battery other components, ingredient, excellent chemical property is shown.
Above-mentioned gallium, indium, tin purity be higher than 99.8% or more, avoid may cause self discharge because mixing other impurities
Bring capacity attenuation is too fast.
Preferably, silicon is the active material of cathode, specifically can be nano-silicon, micron silicon, aoxidizes sub- silicon, silicon-carbon, SiOx
At least one of.Under the action of aforementioned liquid metal nanoparticle, it is related to the material of silicon and the material that volume expansion is big,
It can be used as negative electrode active material of the invention.
Preferably, the binder is acrylic resin, in sodium alginate, sodium carboxymethylcellulose, Kynoar
It is any.These binders are the common binder of field of lithium ion battery, can be well by silicon materials, liquid metal nanometer
Particle is bonded in negative current collector surface.
Liquid metal matrix self-healing lithium cell negative pole provided by the invention does not need to add additional conductive agent, but directly with
Liquid metal nano particle improves the content of silicon materials, is used for lithium ion battery as self-repair material and conductive agent
When upper, there is good interfacial contact and ultralow resistivity, liquid metal nano particle can carry out self to silicon materials
It repairs, to realize overlength cycle characteristics, and quick charge may be implemented, high-multiplying power discharge can be carried out.
Correspondingly, the present invention also provides the preparation methods of liquid metal matrix self-healing lithium cell negative pole.In one embodiment, institute
State preparation method the following steps are included:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, is obtained liquid metal and is received
The composite material of rice grain and silicon；
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, is made
The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing, obtain liquid metal matrix by slurry
Self-healing lithium cell negative pole.
Detailed explanation is done to the preparation method of liquid metal matrix self-healing lithium cell negative pole below.
Specifically, in the suspension of above-mentioned liquid metal nano particle, dispersion liquid is methanol, ethyl alcohol, appointing in isopropanol
One kind, these types of dispersion liquid have a good dispersion effect to liquid metal nano particle, and mix point with silicon materials
It dissipates after composite material is made, also facilitates removal.
Preferably, mercaptan dispersing agent is also contained in the suspension, by the effect of mercaptan, so that liquid metal nanometer
Grain dispersibility is more preferable.
Specifically, the suspension of liquid metal nano particle can be prepared using following method:
Be gallium by mass ratio: indium: tin=(6~9): (1~3): 1 gallium indium tin mixture carries out mixing place with dispersion liquid
Reason, while mercaptan dispersing agent is added, and pass through Ultrasonic Pulverization, obtain the suspension of liquid metal nano particle.
When carrying out Ultrasonic Pulverization to liquid metal nano particle, ultrasonic power is not less than 400W, and ultrasonic time is not less than
20min, the temperature condition of ultrasonic treatment are 15~30 DEG C, and 5~10s of each ultrasound stands 3~5s, is ultrasonically treated 20min repeatedly
Or more, it can be obtained partial size in the liquid metal nano particle suspension of 5~200nm.
Preferably, the proportion of liquid metal nano particle and dispersion liquid is 1g:(200~300 in the suspension) mL,
Under the ratio, liquid metal nano particle dispersion flows are good, and are convenient for subsequent removal dispersion liquid.
In step S01, the time that the suspension of liquid metal nano particle and silicon powder are ultrasonically treated is 10~
60min is then evaporated at 40~100 DEG C, natural cooling, can be obtained the composite material of liquid metal nano particle and silicon.
In step S02, the solvent of the composite material for dispersing binder and the liquid metal and silicon is methanol, second
Any one of alcohol, isopropanol.Wherein binder is acrylic resin, sodium alginate, sodium carboxymethylcellulose, Kynoar
Any one of.It is not reinflated detailed using the mixing paste technology that lithium ion battery is common, therefore herein in mixing process
Thin description.
Preferably, the slurry viscosity of acquisition is 1.5 × 10-3~1.5Pas can obtain good painting under the viscosity
Cover effect.
Slurry is coated on the drying process behind negative current collector surface by the present invention, is preferably dried in vacuo, vacuum drying can
Effectively to avoid the generation of other side reactions.It is further preferred that 80~150 DEG C of vacuum drying temperature, the time is 6~for 24 hours.
The surface density of the negative electrode of lithium ion battery obtained as a result, is 3~5mg/cm2.Under the surface density, manufactured lithium
Ion battery electrochemical performance, especially long circulation life, after reaching 1500 times, battery capacity conservation rate still can be high
Up to 80% or more.
The preparation method of liquid metal matrix self-healing lithium cell negative pole of the present invention, preparation process is few, high production efficiency, Cheng Chancheng
This is low, and seamless connection, easily realization industrialization can be realized with present industry line.
Since liquid metal matrix self-healing lithium cell negative pole provided by the invention has above-mentioned excellent characteristics, the present invention
Furthermore provide a kind of lithium ion battery.The lithium ion battery has anode, cathode, diaphragm, electrolyte and battery case,
Middle cathode is the above-mentioned liquid metal matrix self-healing lithium cell negative pole provided of the present invention, and anode, diaphragm, electrolyte and battery case are
The common material of technical field of lithium ion, therefore not reinflated detailed description herein.
Lithium ion battery provided by the invention can be effective since cathode uses liquid metals base self-healing lithium cell negative pole
Ground improves the coulombic efficiency of lithium ion battery, and carries out selfreparing to silicium cathode material by liquid metal, avoids SEI film
It is unstable, it is contacted in conjunction with liquid metal with the good interface of silicon materials and the super-low resistivity of liquid metal, realizes lithium ion
The high power charging-discharging and long circulation life of battery.
More effectively to illustrate technical solution of the present invention, technical side of the invention is illustrated below by specific embodiment
Case.
Embodiment 1
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle isopropanol suspension:
By 0.5g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten
In the isopropanol of 100mL, 2.0mg mercaptan dispersing agent is added, it is still aging then in ultrasonic disintegrator ultrasonic vibration 60min
5h obtains gallium indium tin liquid metal nano particle isopropanol suspension.
(2) preparation of the composite material of liquid metal nano particle and nano silicon particles:
The gallium indium tin liquid metal nano particle isopropanol suspension and 0.5g nano-silicon powder that step (1) is obtained carry out
Mixing, the average diameter 80nm of nano-silicon, the Ultrasonic Pulverization 20min at 20 DEG C in ultrasonic disintegrator, wherein every Ultrasonic Pulverization 5s,
3s is stood, ultrasonic disintegrator probe diameter 19mm, ultrasonic power 1100W fill liquid metal nano particle with nano silicon particles
Divide after mixing, be evaporated at 80 DEG C, scraping residual powder obtains the composite material of liquid metal nano particle and nano silicon particles.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
Composite material, the 0.2g10wt% of liquid metal nano particle and nano silicon particles that 0.18g step (2) is obtained
Acrylic resin soln and 0.5mL isopropanol carry out mixing treatment together, for magnetic agitation to uniform slurry is obtained, slurry is viscous
About 3 × 10-1Pa·s；Then slurry is poured on copper foil, is spread out slurry blade coating with 50 μm of scrapers, after natural drying
It is dry to be put into vacuum oven, vacuum oven temperature sets 120 DEG C, soaking time 12h, and the pole piece after drying is cut into diameter
The pole piece of 12mm is stand-by.
Embodiment 2
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle alcohol suspending liquid:
By 1.0g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten
In the ethyl alcohol of 250mL, 5.0mg mercaptan dispersing agent is added, then in ultrasonic disintegrator ultrasonic vibration 60min, still aging 5h,
Obtain gallium indium tin liquid metal nano particle alcohol suspending liquid.
(2) preparation of the composite material of liquid metal nano particle and micron silicon particle:
The gallium indium tin liquid metal nano particle alcohol suspending liquid that step (1) obtains is mixed with 1.5g microns of Si powders
It closes, 2 μm of the average diameter of micron silicon, the Ultrasonic Pulverization 120min at 25 DEG C in ultrasonic disintegrator, wherein every Ultrasonic Pulverization 5s, quiet
3s, ultrasonic disintegrator probe diameter 6mm, ultrasonic power 400W are set, liquid metal nano particle and micron silicon particle is sufficiently mixed
It after even, is evaporated at 100 DEG C, scraping residual powder obtains the composite material of liquid metal nano particle and micron silicon particle.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
Composite material, the 0.4g10wt% of liquid metal nano particle and micron silicon particle that 0.36g step (2) is obtained
Acrylic resin soln and 1.5mL isopropanol carry out mixing treatment together, for magnetic agitation to uniform slurry is obtained, slurry is viscous
About 0.5Pas；Then slurry is poured on copper foil, slurry blade coating is spread out with 50 μm of scrapers, is put into after natural drying
Vacuum oven is dry, and vacuum oven temperature sets 100 DEG C, and soaking time is cut into diameter 12mm for 24 hours, by the pole piece after drying
Pole piece it is stand-by.
Embodiment 3
A kind of preparation method of liquid metal matrix self-healing lithium electrode, comprising the following steps:
(1) preparation of gallium indium tin liquid metal nano particle methanol suspension:
By 2.0g purity be above 99.9% and mass ratio be gallium: indium: tin=7:2:1 gallium, indium, tin metal mixture are molten
In the methanol of 500mL, 5.0mg mercaptan dispersing agent is added, it is still aging then in ultrasonic disintegrator ultrasonic vibration 100min
5h obtains gallium indium tin liquid metal nano particle methanol suspension.
(2) preparation of the composite material of liquid metal nano particle and silicon carbide particles:
The gallium indium tin liquid metal nano particle methanol suspension that step (1) obtains is mixed with 2.0g silicon-carbon powder
It closes, the average grain diameter of gallium indium tin liquid metal nano particle is 1000nm, and the average diameter of silicon-carbon powder is 10 μm, in ultrasonic powder
Ultrasonic Pulverization 60min at 15 DEG C in broken machine, wherein every Ultrasonic Pulverization 5s, stands 3s, ultrasonic disintegrator probe diameter 6mm, ultrasound
Power 400W is evaporated at 60 DEG C after mixing well liquid metal nano particle and silicon carbide particles, and scraping residual powder obtains
The composite material of liquid metal nano particle and silicon carbide particles.
(3) preparation of liquid metal matrix self-healing lithium cell negative pole:
The composite material of liquid metal nano particle and silicon carbide particles that 0.9g step (2) is obtained, 0.1g10wt%
Acrylic resin soln and 0.3mL isopropanol carry out mixing treatment together, and for magnetic agitation to uniform slurry is obtained, slurry is viscous about
For 1Pas；Then slurry is poured on copper foil, slurry blade coating is spread out with 100 μm of scrapers, is put into after natural drying true
Empty drying box is dry, and vacuum oven temperature sets 60 DEG C, soaking time 12h, and the pole piece after drying is cut into diameter 12mm's
Pole piece is stand-by.
In order to verify the microscopic appearance and other performances of the cathode that Examples 1 to 3 obtains, corresponding property is carried out to it respectively
It can detect, specifically include scanning electron electron-microscope scanning (SEM) and lithium ion battery progress cycle performance, coulombic efficiency is made etc.
The test of aspect.
(1) SEM is tested
According to the mode of operation that conventional SEM is scanned, specific test result is as shown in figs. 2 to 4.
Wherein, Fig. 2 is that the cathode that embodiment 1 obtains amplifies 5000 times of SEM figure, and Fig. 3 is that embodiment 2 amplifies 10000 times
SEM figure, Fig. 4 be embodiment 3 amplify 500 times SEM figure.By Fig. 2~4 it is found that liquid metal respectively with silicon nanoparticle, micro-
Rice silicon particle, silicon carbide particles are evenly dispersed, and pole piece structure is completely without obvious crackle.
(2) cycle performance, high rate performance and coulombic efficiency test
Half-cell is assembled with the cathode of embodiment 1 and metal lithium sheet, is 8A/g's in current density after button cell is made
Under the conditions of carry out charge-discharge test with the test of, different multiplying and coulombic efficiency test, test result is as shown in Fig. 5,6,7.
As can be seen from Figure 5, the half-cell assembled has the electrochemistry circulating ring number of overlength, can protect after 200 circle circulations
90% or more capacity is held, and still there is 82% capacity retention ratio after 1500 charge and discharge electric circles circulation.Illustrate the present invention
The cathode that embodiment 1 obtains can effectively mention the cycle performance of battery, and as can be known from Fig. 6, battery has the forthright again of superelevation
Can, in 20A g-1When be 360mAh g-1, fully charged in 65 seconds/electric discharge has ultrafast charge-discharge performance.As can be seen from Figure 7
Since liquid metal is during silicon particle expands, the stress by silicon particle is squeezed, and destroys liquid metal particle
Insulation sheath, the liquid metal outflow disperse with high conductivity and high fluidity for being is around silicon particle, spontaneous realization
Liquid metal conductive network and can the problem of Cracking that occurs in cyclic process of spontaneous reparation silicon, and at the same time liquid metal pair
The gap of silicon particle cluster realizes preferable filling and cladding, the area of exposure in the electrolytic solution is reduced, to reduce
The increment of SEI film, the coulombic efficiency for improving first circle and then recycling.
Since the cathode performance that preparation method of the invention obtains is stablized, homogeneity is good, therefore does not carry out to embodiment 2,3
Corresponding electrochemical property test.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (9)
1. a kind of liquid metal matrix self-healing lithium cell negative pole including negative current collector and is attached to the negative current collector surface
Negative electrode material, which is characterized in that the negative electrode material includes the composite material of liquid metal nano particle and silicon, binder；
According to mass ratio, the composite material of the liquid metal nano particle and silicon: binder=(9~90): 1；
Wherein, in the composite material of the liquid metal nano particle and silicon, the mass ratio of liquid metal nano particle and silicon is
1:(1~5).
2. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the liquid metal nanometer
Grain is the mixture of gallium, indium, tin, and the mass ratio of the gallium, indium, tin is (6~9): (1~3): 1.
3. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the silicon is nano-silicon, micro-
Rice silicon aoxidizes sub- silicon, silicon-carbon, SiOxAt least one of.
4. liquid metal matrix self-healing lithium cell negative pole as described in claim 1, which is characterized in that the binder is acrylic acid
Any one of resin, sodium alginate, sodium carboxymethylcellulose, Kynoar.
5. such as the preparation method of the described in any item liquid metal matrix self-healing lithium cell negative poles of Claims 1 to 4, feature exists
In at least including the following steps:
The suspension of liquid metal nano particle is ultrasonically treated by step S01. with Si powder, obtains liquid metal nanometer
The composite material of grain and silicon；
Step S02. disperses the composite material of binder and the liquid metal nano particle and silicon in solvent, and slurry is made
The slurry of acquisition is then coated on negative current collector surface, through drying, cuts processing by material, obtains liquid metal matrix certainly
Heal lithium cell negative pole.
6. the preparation method of liquid metal matrix self-healing lithium cell negative pole as claimed in claim 5, which is characterized in that the liquid
The dispersion liquid of the suspension of metal nanoparticle is any one of methanol, ethyl alcohol, isopropanol, contains mercaptan in the suspension
Dispersing agent, the proportion of liquid metal nano particle and dispersion liquid is 1g:(200~300 in the suspension) mL.
7. the preparation method of liquid metal matrix self-healing lithium cell negative pole as claimed in claim 5, which is characterized in that the solvent
For any one of methanol, ethyl alcohol, isopropanol；And/or the viscosity of the slurry is 1.5 × 10-3~1.5Pas.
8. a kind of lithium ion battery, including anode, cathode, diaphragm, electrolyte and battery case, which is characterized in that the cathode is
The described in any item liquid metal matrix self-healing lithium cell negative poles of Claims 1 to 4 or the cathode use such as claim 5
The preparation method of~7 described in any item liquid metal matrix self-healing lithium cell negative poles is prepared.
9. lithium ion battery as claimed in claim 8, which is characterized in that the surface density of the negative electrode of lithium ion battery be 3~
5mg/cm2。
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