CN108346523A - A kind of preparation method containing lithium an- ode of mixed type energy storage device - Google Patents
A kind of preparation method containing lithium an- ode of mixed type energy storage device Download PDFInfo
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- CN108346523A CN108346523A CN201810149093.2A CN201810149093A CN108346523A CN 108346523 A CN108346523 A CN 108346523A CN 201810149093 A CN201810149093 A CN 201810149093A CN 108346523 A CN108346523 A CN 108346523A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004146 energy storage Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 61
- 239000011149 active material Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000005098 hot rolling Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 210000000170 cell membrane Anatomy 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 244000050510 Cunninghamia lanceolata Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SWWQQSDRUYSMAR-UHFFFAOYSA-N 1-[(4-hydroxyphenyl)methyl]-1,2,3,4-tetrahydroisoquinoline-6,7-diol;hydrochloride Chemical group Cl.C1=CC(O)=CC=C1CC1C2=CC(O)=C(O)C=C2CCN1 SWWQQSDRUYSMAR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000003466 welding Methods 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods containing lithium an- ode for the mixed type energy storage device for belonging to electrochemical energy storage technical field.Including：Negative electrode active material, elastic binder, conductive agent, additive, stabilized lithium powder etc. are subjected to mixing dispersion, to form mixture；Roll-in is carried out to the mixture, to form film containing lithium an- ode；Conducting resinl is applied and forms conductive adhesive coating on a current collector；It is compound that film containing lithium an- ode and the collector for forming conductive adhesive coating are subjected to hot pressing.Lithium an- ode film will be contained, and with lithium ion cell positive, either lithium ion battery or lithium-ion capacitor are made in the matching of ultracapacitor activated carbon electrodes.The present invention can be used for the production of super-capacitor pole piece, the production of electrodes of lithium-ion batteries, in the production process of the contour elastic electrode of production of fuel cell pole piece.It can be mass produced, and solvent-free volatilization causes environmental pollution in production process, greatly reduces cost, speed of production is fast, and manufacturing cost is low.
Description
Technical field
The present invention relates to electrochemical energy storage technical field, more particularly to a kind of mixed type energy storage device contains lithium an- ode
Preparation method.
Background technology
Electrochemical power source has received extensive use as energy storage component, with the hair of China's electrical source of power industry
Exhibition, it is increasing to the demand of electrochemical power source, it is higher and higher to its performance requirement.Electrode is the core of electrochmical power source, electricity
Pole performance parameter determines the performance of power supply itself, is to be used as energy storage for lithium ion insertion and abjection reaction containing lithium an- ode
The power supply of principle has important meaning.Lithium ion battery is made with the matching of lithium ion anode electrode containing lithium an- ode, it can be significantly
First charge-discharge efficiency is improved, to improving the energy density of battery, there is very big help.Containing lithium an- ode with activated carbon electrodes
With combination, novel energy-storing component is formed, anode is to carry out energy storage, the insertion that cathode passes through lithium ion by adsorption charge
Abjection carries out energy storage, combines the principle of lithium ion battery and ultracapacitor, forms mixed type energy storage device-lithium ion super
Capacitor.
Invention content
The object of the present invention is to provide disclose a kind of preparation method containing lithium an- ode of mixed type energy storage device, feature
It is, includes the following steps：
（1）Active material, elastic binder, conductive agent, stabilized lithium powder are subjected to mixing dispersion, to form mixture；It is mixed
The gross mass of conjunction dispersed mixture, which forms, includes：Elastic binder is 1 wt %-20 wt %, and conductive agent is 0.5 wt %-30
Wt %, active material are 50 wt %-98 wt %, and stabilized lithium powder is 0.5 wt %-10 wt %；
（2）To step（1）Mixture after acquired mixing dispersion carries out multiple roll-in, to form film containing lithium an- ode；
（3）Conductive agent is applied and forms conductive adhesive coating on a current collector；
（4）The progress hot pressing of the collector of film containing lithium an- ode and conductive adhesive coating is compound, it obtains high resiliency and contains lithium metal
Negative electrode film；
（5）Lithium an- ode film will be contained and make lithium ion with lithium ion cell positive or the matching of ultracapacitor activated carbon electrodes
Battery or lithium ion super capacitor.
The active material is powder, 0.1 μm to 2 μm of particle size range, and it includes activated carbon, airsetting to choose active material
Glue charcoal, carbon nanotube, Modified Activated Carbon nano-tube material, graphene, modified graphene material, activated carbon and graphene composite material,
Activated carbon and carbon nanotube composite material, carbonaceous mesophase spherules, natural graphite, modified graphite, coated graphite, artificial graphite, coke
The positive pole powder material containing elemental lithium, the negative electrode of lithium ion battery that charcoal, silica flour, silicon line lithium ion battery use use first containing lithium
The mixture of the one or more of the cathode powder body material of element.
The elastic binder is solid or powder, the binder that molecular weight is 10 ten thousand to 100 ten thousand, and selection three
First EP rubbers, acrylic acid build resin, polytetrafluoroethylene (PTFE), Kynoar, butadiene-styrene rubber, nitrile rubber demethyl sodium cellulosate
One or more mixture.
The conductive agent be powder, acetylene black, Ketjen black, conductive fiber, electrically conductive graphite, wire one kind or one kind with
On mixture.
The additive is rubber or plastic processing additives；And choose reinforcing agent, antiaging agent, vulcanizing agent, plasticizer
One or more mixture.
The stable metal lithium powder is the SLMP of FMC Corp. of U.S. production, and purity 97%, size is 5 to 50 μm.
The step 1）Mixing dispersing mode disperseed using open double rods mixing dispersion, the sealed mixing of single screw rod,
The sealed mixing dispersion of twin-screw, the sealed mixing dispersion of multiscrew, double planetary mixing dispersion, the mixing dispersion of ball milling formula；It is mixed
It is 5 to 360 minutes to close jitter time.
The step 2）Mixture carry out roll-in use Hot-rolling process；Roll temperature is 120 DEG C -200 DEG C；To mixture
Multiple hot-rolling pressure is carried out, to form continuous elastomeric film containing lithium an- ode.
The collector is selected from copper foil, aluminium foil or sticking conductive polymer film.
The conducting resinl is glued by one or more of conductive black, electrically conductive graphite, graphene, carbon nanotube with water system
Either oil system binder is tuned into paste and is formed in collection liquid surface by intaglio plate coating or bar rubbing method solid-state like for knot agent
Conductive adhesive coating.
The beneficial effects of the invention are as follows the production that can be used for super-capacitor pole piece, the production of electrodes of lithium-ion batteries,
In the production process of the contour elastic electrode of production of fuel cell pole piece.It can be mass produced, and in production process
Solvent-free volatilization causes environmental pollution, greatly reduces cost, speed of production is fast, and manufacturing cost is low.
Description of the drawings
Fig. 1 is the flow diagram for preparing high resiliency electrode.
Fig. 2 is the anode pole piece scanning electron microscope (SEM) photograph of embodiment 1.
Fig. 3 is the cathode pole piece scanning electron microscope (SEM) photograph of embodiment 2.
Fig. 4 is the device charging and discharging curve figure of embodiment 3.
Specific implementation mode
The present invention provides a kind of preparation method containing lithium an- ode of mixed type energy storage device, includes the following steps：
（1）Active material, elastic binder, conductive agent, additive and stabilized lithium powder are subjected to mixing dispersion, to form mixing
Object；
（2）To step（1）Mixture after acquired mixing dispersion carries out multiple roll-in, to form film containing lithium an- ode；
（3）Conducting resinl is applied and forms conductive adhesive coating on a current collector；
（4）The progress hot pressing of the collector of film containing lithium an- ode and conductive adhesive coating is compound, it obtains high resiliency and contains lithium metal
Negative electrode film；
（5）Lithium an- ode film will be contained and make mixed type with lithium ion cell positive or the matching of ultracapacitor activated carbon electrodes
Lithium ion battery or mixed type lithium ion super capacitor.
Fig. 1 show the flow diagram for preparing high resiliency electrode.The preparation method of the high resiliency electrode includes step
It is as follows：
1）Active material, high resiliency binder, conductive agent are first subjected to mixing dispersion, stabilized lithium powder to form mixture；Institute
The gross mass for stating mixture includes 1 wt %-20 wt % of high resiliency binder, 0.5 wt %-30 wt % of conductive agent, activity
50 wt %-98 wt % of substance, stabilized lithium powder are 0.5 wt %-10 wt %.
2）Mixture after disperseing to mixing carries out roll-in, and mixing dispersion process carries out about 5 to 360 minutes, roll temperature
It is 120 DEG C -200 DEG C；Multiple hot-rolling pressure is carried out to mixed material, contains lithium an- ode to form continuous high resiliency activity
Film.
3）Conducting resinl is applied to form conductive adhesive coating；
4）The collector progress hot pressing that high resiliency active matter plasma membrane and surface are formed to conductive adhesive coating is compound, obtains high resiliency
Porous electrode.
" high resiliency electrode " of the present invention means to be piled by little particle and sticks in one piece by high resiliency binder and have
The electrode of high resiliency performance, in favor of adapting to the variation of material volume dilation in device assembling and reaction process.In electrode plus
A small amount of additive is added during work, the processing performance of high electrode can be led to, improve the flexibility of electrode, improve the resistance to ring of electrode
Border performance.
" conductive agent " means to ensure that electrode has good charge-discharge performance, is usually added into when pole piece makes
A certain amount of conductive materials play the role of collected current, to subtract between active material, between active material and collector
The contact resistance of small electrode accelerates the transfer rate of electronics, adsorbs more electrolyte, effectively improves ion in electrode material
Migration rate, to improve the efficiency for charge-discharge of electrode.
" conducting resinl " has the adhesive of certain conducting function at a certain temperature after meaning solidification or drying；It is described
Conducting resinl is by one or more of conductive black, electrically conductive graphite, graphene, carbon nanotube with water-based binder or oil system
Binder is tuned into paste, and is coated in collection liquid surface by intaglio plate coating or bar rubbing method and forms solid-state like conductive adhesive
Coating.
" collector " means that the structure or part for collecting electric current, function mainly produce electroactive substance
Raw electric current collects to form larger current versus output.In example scheme, the active material is powder shape
Formula.
The active material is powder, 0.1 μm to 2 μm of particle size range, including activated carbon, aeroge charcoal, carbon nanotube, is changed
Property carbon nanotube material, graphene, modified graphene material, activated carbon and graphene composite material, activated carbon and carbon nanotube
Composite material, carbonaceous mesophase spherules, natural graphite, modified graphite, coated graphite, artificial graphite, coke, silica flour, silicon line lithium from
The cathode powder body material containing elemental lithium that the positive pole powder material containing elemental lithium, the negative electrode of lithium ion battery that sub- battery uses use
The mixture of middle one or more.
The high resiliency binder is solid or powder, and preferred molecular weight is 10 ten thousand to 100 ten thousand binder, and wraps
Include ethylene propylene diene rubber, acrylic resin, polytetrafluoroethylene (PTFE), Kynoar, butadiene-styrene rubber, nitrile rubber demethyl cellulose
One or more of mixture in sodium.
The conductive agent is powder；Including a kind of or several in acetylene black, Ketjen black, conductive fiber, electrically conductive graphite, wire
The mixture of kind.
The mixing dispersing mode of the present invention includes open double rod mixing dispersions, the sealed mixing dispersion of single screw rod, double spiral shells
The sealed mixing dispersion of bar, the sealed mixing dispersion of multiscrew, double planetary mixing dispersion, the mixing dispersion of ball milling formula.
The collector of the present invention uses copper foil, aluminium foil or sticking conductive polymer film；And pass through intaglio plate coating
Or conducting resinl is coated in collection liquid surface and forms solid-state like conductive adhesive coating by bar rubbing method.
With reference to the accompanying drawings, the present invention is explained in detail by following embodiment.
Embodiment 1
Using the activated carbon that PCT companies of South Korea produce as active material, specific surface area is 1850 to 2150 ㎡/g, and D50 is
1-2μm。
The carbonaceous mesophase spherules produced using Shanghai China fir China fir, specific discharge capacity 330mAh/g, irreversible specific capacity are
20mAh/g。
Using the ethylene propylene diene rubber particle that Dow produces as binder, D50 is 0.25 μm.
Using the Super P of Changzhou Te Migao companies as conductive agent.
Using the SN-307R that auspicious father-in-law produces as conducting resinl.
Using the 2400 type diaphragms that celgard is produced as battery diaphragm
The stable metal lithium powder SLMP produced using FMC Corp. of the U.S.
The ethylene propylene diene rubber particle of the activated carbon (active material) of above-mentioned South Korea PCT companies production, Dow production is (viscous
Tie agent), the SP (conductive agent) of Changzhou Te Migao companies production weighs by quality, stable metal lithium powder SLMP, mass ratio 85：
9.5:4.5:1, the above substance carries out ball milling dispersion using ball-milling dispersion machine, and dispersion process carries out 60 minutes, obtains the dispersion of 1kg
Mixture；Hot press roll-in is carried out to being formed by mixture, 180 DEG C of roller temperature, roll-in forms active matter plasma membrane three times；With aluminium foil
As collector, waterborne conductive glue SN-307R is coated on aluminium foil using gravure coating process, to form conductive coating；Will
The copper foil progress of the conductive coating of the active matter plasma membrane and formation that arrive is compound, waits for the solvent volatilization in active matter plasma membrane and conducting resinl
It finishes, that is, forms dry high resiliency porous electrode.The scanning electricity of obtained high resiliency porous electrode pole piece as shown in Figure 2
Mirror figure.
Embodiment 2
The carbonaceous mesophase spherules of Shanghai China fir China fir production, the ethylene propylene diene rubber particle of Dow production, Changzhou Te Migao companies
The SP of production, stable metal lithium powder SLMP, weighs by quality, mass ratio 90：7:2:1, the above substance is disperseed using ball milling
Machine carries out ball milling dispersion, and dispersion process carries out 120 minutes, obtains the dispersed mixture of 1kg；Heat is carried out to being formed by mixture
Press roll-in, 180 DEG C of roller temperature, roll-in three times, form active matter plasma membrane；It, will using gravure coating process using copper foil as collector
Waterborne conductive glue SN-307R is coated on aluminium foil, to form conductive coating；By obtained active matter plasma membrane and the conductive painting formed
The copper foil progress of layer is compound, waits for that the volatilization of the solvent in active matter plasma membrane and conducting resinl finishes, that is, it is porous to form dry high resiliency
Electrode.The scanning electron microscope (SEM) photograph of obtained high resiliency porous electrode pole piece as shown in Figure 3.
Embodiment 3
The embodiment 1 or 2 obtained high resiliency porous electrode pole piece of embodiment is in blocks as positive and negative anodes pole piece trimming, with
Diaphragm assembles together, and carries out postorder welding, encapsulation, baking, fluid injection, chemical conversion, test step, completes element manufacturing, device
Charging and discharging curve is as shown in Figure 4.
Claims (10)
1. a kind of preparation method containing lithium an- ode of mixed type energy storage device, which is characterized in that include the following steps：
（1）Active material, elastic binder, conductive agent, stabilized lithium powder are subjected to mixing dispersion, to form mixture；It is mixed
The gross mass of conjunction dispersed mixture, which forms, includes：Elastic binder is 1 wt %-20 wt %, and conductive agent is 0.5 wt %-30
Wt %, active material are 50 wt %-98 wt %, and stabilized lithium powder is 0.5 wt %-10 wt %；
（2）To step（1）Mixture after acquired mixing dispersion carries out multiple roll-in, to form film containing lithium an- ode；
（3）Conductive agent is applied and forms conductive adhesive coating on a current collector；
（4）The progress hot pressing of the collector of film containing lithium an- ode and conductive adhesive coating is compound, it obtains high resiliency and contains lithium metal
Negative electrode film；
（5）Lithium an- ode film will be contained and make lithium ion with lithium ion cell positive or the matching of ultracapacitor activated carbon electrodes
Battery or lithium ion super capacitor.
2. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
It is powder to state active material, 0.1 μm to 2 μm of particle size range, and it includes that activated carbon, aeroge charcoal, charcoal are received to choose active material
Mitron, Modified Activated Carbon nano-tube material, graphene, modified graphene material, activated carbon and graphene composite material, activated carbon and charcoal
Nanometer tube composite materials, carbonaceous mesophase spherules, natural graphite, modified graphite, coated graphite, artificial graphite, coke, silica flour, silicon
The negative electrode powder containing elemental lithium that the positive pole powder material containing elemental lithium, the negative electrode of lithium ion battery that line lithium ion battery uses use
The mixture of the one or more of body material.
3. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
It is solid or powder to state elastic binder, and molecular weight is 10 ten thousand to 100 ten thousand binder, and chooses ethylene-propylene-diene monomer
One kind or one of glue, acrylic resin, polytetrafluoroethylene (PTFE), Kynoar, butadiene-styrene rubber, nitrile rubber demethyl sodium cellulosate
Kind or more mixture.
4. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
It is powder, the mixing of acetylene black, the one or more of Ketjen black, conductive fiber, electrically conductive graphite, wire to state conductive agent
Object.
5. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
It is rubber or plastic processing additives to state additive；And choose reinforcing agent, antiaging agent, vulcanizing agent, one kind of plasticizer or one
Kind or more mixture.
6. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
The SLMP that stable metal lithium powder is the production of FMC Corp. of the U.S., purity 97% are stated, size is 5 to 50 μm.
7. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
State step 1）Mixing dispersing mode sealed using open double rods mixing dispersion, the sealed mixing dispersion of single screw rod, twin-screw
Formula mixing dispersion, the sealed mixing dispersion of multiscrew, double planetary mixing dispersion, the mixing dispersion of ball milling formula；Mix jitter time
It is 5 to 360 minutes.
8. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
State step 2）Mixture carry out roll-in use Hot-rolling process；Roll temperature is 120 DEG C -200 DEG C；Mixture is carried out repeatedly
Hot-rolling pressure, to form continuous elastomeric film containing lithium an- ode.
9. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that institute
It states collector and is selected from copper foil, aluminium foil or sticking conductive polymer film.
10. a kind of preparation method containing lithium an- ode of mixed type energy storage device according to claim 1, which is characterized in that
The conducting resinl by one or more of conductive black, electrically conductive graphite, graphene, carbon nanotube with water-based binder or
Oil system binder is tuned into paste, and forms solid-state like conduction in collection liquid surface by intaglio plate coating or bar rubbing method and glue
Property coating.
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| CN109003823A (en) * | 2018-08-08 | 2018-12-14 | 上海奥威科技开发有限公司 | The manufacturing method of lithium-ion capacitor with the high power charging-discharging ability long-life |
| CN111164802A (en) * | 2018-08-10 | 2020-05-15 | 株式会社Lg化学 | Negative electrode for lithium metal battery, method for producing the same, and lithium metal battery comprising the same |
| WO2020125562A1 (en) * | 2018-12-19 | 2020-06-25 | 深圳先进技术研究院 | Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment |
| CN112038579A (en) * | 2020-09-28 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Metal lithium composite electrode, preparation method thereof and electrochemical energy storage device |
| CN112447936A (en) * | 2019-08-28 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Negative pole piece and lithium secondary battery thereof |
| WO2021195835A1 (en) * | 2020-03-30 | 2021-10-07 | 中能中科（天津）新能源科技有限公司 | Pre-lithiated negative electrode and preparation method therefor, and lithium ion battery and supercapacitor having pre-lithiated negative electrode |
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| CN112038579A (en) * | 2020-09-28 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Metal lithium composite electrode, preparation method thereof and electrochemical energy storage device |
| WO2022159985A1 (en) * | 2021-01-25 | 2022-07-28 | Blue Current, Inc. | Solid-state lithium ion multilayer battery and manufacturing method |
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| WO2023225937A1 (en) * | 2022-05-26 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Negative electrode plate and preparation method therefor, secondary battery, battery module, battery pack and electric device |
| CN114843448A (en) * | 2022-06-09 | 2022-08-02 | 远景动力技术(江苏)有限公司 | Method for relieving corrosion of electrode plate, electrode plate and lithium ion battery |
| CN116799155A (en) * | 2023-06-27 | 2023-09-22 | 肇庆理士电源技术有限公司 | Dry electrode manufacturing method of negative electrode artificial graphite material |
| CN116799155B (en) * | 2023-06-27 | 2023-12-19 | 肇庆理士电源技术有限公司 | Dry electrode manufacturing method of negative electrode artificial graphite material |
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