CN105023752B - Printed flexible electrolytic capacitor and manufacturing method thereof - Google Patents
Printed flexible electrolytic capacitor and manufacturing method thereof Download PDFInfo
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- CN105023752B CN105023752B CN201410174909.9A CN201410174909A CN105023752B CN 105023752 B CN105023752 B CN 105023752B CN 201410174909 A CN201410174909 A CN 201410174909A CN 105023752 B CN105023752 B CN 105023752B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000007639 printing Methods 0.000 claims abstract description 5
- 230000004888 barrier function Effects 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 230000036647 reaction Effects 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 241000238631 Hexapoda Species 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000000123 paper Substances 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011370 conductive nanoparticle Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 4
- 230000002335 preservative effect Effects 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001006 Constantan Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000691 Re alloy Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 229910001195 gallium oxide Inorganic materials 0.000 description 4
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000003854 Surface Print Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a printed flexible electrolytic capacitor and a manufacturing method thereof, wherein the printed flexible electrolytic capacitor comprises: the device comprises a flexible anode supporting substrate, an anode made of low-melting-point metal ink printed on the anode substrate, an insulating layer dielectric formed after an anode metal film is oxidized through an electrolytic process, an electrolyte serving as a cathode and the flexible cathode supporting substrate. According to the printed electrolytic capacitor and the manufacturing method thereof, the low-melting-point liquid metal ink is introduced and the oxide insulating layer is manufactured through an electrolytic process, so that the whole printed electrolytic capacitor can be directly manufactured in a printing mode, and the printed substrate adopts a flexible substrate and can be manufactured into a wearable high-capacity capacitor battery; the whole manufacturing process has low requirement on environment and can be finished under normal temperature and conventional conditions, so that the complexity of the electrolytic capacitor manufacturing process is obviously reduced, the manufacturing efficiency is greatly improved, and the cost is reduced.
Description
Technical field
The present invention relates to electric capacity manufacture technology field, more particularly to coating and cell reaction are printed by means of low-melting-point metal
A kind of flexible electrochemical capacitor of printing-type and preparation method that mode is realized.
Background technology
Electric capacity is the device for accommodating electric charge, any two is insulated from each other and the conductor that is spaced closely together between may make up
One capacitor.Electric capacity has extensive use in the electronic device, is usually used in energy storage, control, and separated by direct communication, coupling in circuit
In terms of conjunction, bypass, filtering, resonant tank.Wherein, accumulation energy type capacitor collects electric charge by rectifier, and by the energy of storage
Amount is sent to the output end of power supply by converter lead, thus acts as a kind of battery.According to different power requirements, capacitor
Can be using the mode such as series, parallel or its combination.Capacitor can store electric charge in the presence of outer making alive.Due to being a kind of
Physical energy storage device, electric capacity has the advantages that the charging interval is short, power output is high, long lifespan.
In various electric capacity, electrochemical capacitor be a kind of unit volume capacity can beyond tens of to hundreds times of conventional capacitance electricity
Hold, and cost is relatively low, thus with extensive use.Common electrolytic capacitor uses aluminium or tantalum metal foil as positive pole, with gold
Belong to the insulating oxide of paper tinsel as dielectric, negative electrode is then collectively constituted by conductive material, electrolyte etc., because electrolyte is negative electrode
Major part, electrochemical capacitor therefore and gain the name.So far, the limitation due to manufacture material and process characteristic, such electric capacity are general
It is presented as rigid structure.
Current electrochemical capacitor can realize production mechanization and the automation of scale.Wherein, aluminium electrolutic capacitor master
To be made according to corrosion and two-step process of mutually energizing.Wherein, etching process be dependent on corrosive liquid species, concentration, temperature, former paper tinsel into
Point, paper tinsel speed and power supply type, voltage etc. are carried out in structure, surface state, corrosion process；Technique of energizing then is used to manufacture electricity
Dielectric oxide film.Due to these factors, traditional electrochemical capacitor facility investment is big, and manufacturing process is generally sufficiently complex, consumption energy consumption
Water, and certain environment can be caused to pollute, due to technique limitation, this kind of electrochemical capacitor is difficult to flexible and foldable device is made.Closely
Nian Lai, as a large amount of novel flexible electronic installations include the appearance of wearable device, the demand sharp increase to flexible battery.For
This, if whole manufacture crafts of electrochemical capacitor can be developed into printing-type, is expected to realize flexible electric capacity or even battery, and can be big
The big cost of manufacture for simplifying electrochemical capacitor, so as to meet growing demand.However, can be presented at present with fluid state
Conductive ink extremely lacks, and electrolyte thickness is generally difficult to be made to very thin in electrochemical capacitor, thus can seriously restrict institute's shape
Into electrochemical capacitor capacity.For this reason, it may be necessary to seek feasible way from new technical concept.
The content of the invention
(1) technical problem to be solved
The technical problem to be solved in the present invention is that being difficult realization for existing electrochemical capacitor manufacturing technology directly prints thus
The more difficult deficiency for forming flexible device, there is provided one for introducing low-melting-point metal ink and its ultrathin insulating layer electrolyte electrolysis process
The flexible electrochemical capacitor of kind of printing-type and preparation method, it can be ensured that the quick manufacture of corresponding device, be obviously improved capacity or even technology
Use upper flexibility.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention provides a kind of flexible electrochemical capacitor of printing-type, the printing-type is soft
Property electrochemical capacitor includes：Flexible anode support substrate, anode, insulating barrier dielectric, the electrolyte and Flexible cathodes for serving as negative electrode
Support substrate；The anode is printed on anode base by low melting point liquid metal ink and made；The insulating barrier dielectric is
The insulating barrier dielectric formed after being aoxidized to anode by electrolysis process.
Preferably, the flexible anode support substrate is coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect prevention
One kind in paper, sensing paper, facing paper, pouncing paper, plastics, cloth, malthoid and glass cloth.
Preferably, the anode is to be coated in the film being made on anode support base by low melting point liquid metal ink.
Preferably, the low melting point liquid metal ink be pure gallium or by containing indium, tin, mercury, sodium, potassium, caesium, lead,
One kind in bismuth, tin, copper, aluminium and chromium, it is dissolved in the low temperature multicomponent alloy formed in gallium for two or three；The matter of gallium in the alloy
Amount proportioning is 50%~99%, during remaining composition is indium, tin, mercury, sodium, potassium, caesium, lead, bismuth, tin, copper, aluminium and chromium in the alloy
One kind, two or three；When remaining metal added in gallium is two or three, remaining described intermetallic quality is matched somebody with somebody
Than for any collocation.
Preferably, the insulating barrier dielectric is to be powered after being sprayed water to the anode after impressed cathodic, by cell reaction
The insulating barrier thin dielectric film that technique is formed after anode metal film superficial is aoxidized.
Preferably, the electrolyte for serving as negative electrode is the solution class electrolyte for being close to the insulating barrier thin dielectric film.
Preferably, it is described serve as negative electrode electrolyte be：Carbonic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, barium hydroxide, a water
The one kind closed in ammonia, Kocide SD, sodium chloride, potassium chloride, sodium carbonate, calcium carbonate, sodium acid carbonate, copper sulfate crystal is dissolved in after water
Acid, alkali, the salting liquid class electrolyte of formation.
Preferably, the Flexible cathodes support substrate is coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect prevention
Paper, sensing paper, facing paper, pouncing paper, plastics, cloth, malthoid and one kind in glass cloth are existed by a kind of in these materials
The film that surface coating low-melting-point metal ink is supported.
Preferably, 0.01wt%~80wt% conductive nanometers are contained in the conducting metal ink, electrolyte solution
Grain；The conductive nanoparticle is particle diameter 1nm~900nm platinum, gold, silver, copper, iron, aluminium, antimony, bismuth, cadmium, germanium, nickel, rhodium,
Tantalum, lead, tungsten, rhenium, constantan, tungsten-rhenium alloy or nickel-cadmium, CNT or graphene.
In order to solve the above-mentioned technical problem, the invention provides a kind of method for making the flexible electrochemical capacitor of printing-type, institute
The method of stating is divided into following steps：
Determine flexible anode support substrate and Flexible cathodes support substrate；
The low melting point liquid metal ink is coated on anode support base surface by printing equipment, anode is formed；
Anode surface is sprayed water, water membrane is formed, is attached on the moisture film by a kind of sheet metal in gold, silver, copper
Serve as negative electrode；
Power supply is connected between the anode and negative electrode, cell reaction occurs in moisture film, the oxygen produced at its Anodic
The low-melting-point metal film oxidation of anode surface is formed a thin layer insulating barrier, serves as dielectric by gas；
Remove sheet metal negative electrode；
In insulating barrier dielectric surface spray solution class electrolyte, the negative electrode of electrochemical capacitor is used as；
Flexible cathodes support substrate is attached on electrolyte solution surface；
Low-melting-point metal ink is applied on the Flexible cathodes support substrate surface；
The structure being encapsulated between anode support base, cathode support substrate is fixed using fixture；
Avoid solution from evaporating end encapsulation using silica gel, that is, form electrochemical capacitor；
Repeat the above steps, form multilayer electrochemical capacitor.
(3) beneficial effect
The flexible electrochemical capacitor of the printing-type of the present invention and preparation method, due to introducing low melting point liquid metal ink and electricity
Solution technique so that whole electrochemical capacitor can directly be made in the way of printing, and printed substrates use flexible substrates, can make
Into wearable class or folding capacitor batteries；In addition, the electrolyte thin film thickness that electrolysis process is made is small, thus it is easily formed
Large bulk capacitance；Whole manufacture craft is not high to environmental requirement, can be completed under normal temperature and normal condition, thus significantly reduces
The complexity of electrochemical capacitor preparation technology, increases substantially its producing efficiency and reduces cost.Using this method obtain it is soft
Property electrochemical capacitor, can be widely used for various electronics industry particularly wearable electronic.The technology that the present invention is provided has general
All over meaning, in addition to for making electrochemical capacitor device on a flexible substrate, be also applied for other hard substrates, such as glass, metal,
Timber etc..
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the preparation method steps flow chart of one embodiment according to a kind of flexible electrochemical capacitor of printing-type of the invention
Figure；
Fig. 2 is the flexible electrolytic capacitor of printing-type according to a kind of embodiment 1 of the flexible electrochemical capacitor of printing-type of the invention
Structural representation；
Fig. 3 is the plane formula multilayer electrochemical capacitor knot of the embodiment 2 according to a kind of flexible electrochemical capacitor of printing-type of the invention
Structure schematic diagram；
Fig. 4 is the column formula multilayer electrochemical capacitor knot of the embodiment 3 according to a kind of flexible electrochemical capacitor of printing-type of the invention
Structure schematic diagram.
Embodiment
With reference to Figure of description and embodiment, the embodiment to the present invention is described in further detail.With
Lower embodiment is merely to illustrate the present invention, but can not be used for limiting the scope of the present invention.
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
The invention provides a kind of flexible electrochemical capacitor of printing-type, including：Flexible anode support substrate, anode, insulating barrier
Dielectric, the electrolyte for serving as negative electrode and Flexible cathodes support substrate；The anode is printed on by low melting point liquid metal ink
Anode is made on base；The insulating barrier dielectric is the insulating barrier dielectric formed after being aoxidized to anode by electrolysis process.
Flexible anode support substrate is coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect preservative paper, sensing paper, dress
The one kind adornd in paper, pouncing paper, plastics, cloth, malthoid and glass cloth.Anode is to be coated in sun by low melting point liquid metal ink
The film being made in the support substrate of pole.
Low melting point liquid metal ink is pure gallium or by containing indium, tin, mercury, sodium, potassium, caesium, lead, bismuth, tin, copper, aluminium
With in chromium it is a kind of, be dissolved in the low temperature multicomponent alloy that is formed in gallium for two or three；The quality proportioning of gallium is in the alloy
50%~99%, in the alloy remaining composition be one kind in indium, tin, mercury, sodium, potassium, caesium, lead, bismuth, tin, copper, aluminium and chromium,
Two or three；When remaining metal added in gallium is two or three, remaining described intermetallic quality proportioning is to appoint
Meaning collocation.
Insulating barrier dielectric is to be powered after being sprayed water to the anode after impressed cathodic, by cell reaction technique that anode is golden
The insulating barrier thin dielectric film formed after the superficial oxidation of category film.
The electrolyte for serving as negative electrode is the solution class electrolyte for being close to the insulating barrier thin dielectric film.
The electrolyte for serving as negative electrode is：Carbonic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, barium hydroxide, a hydration ammonia, hydroxide
A kind of in copper, sodium chloride, potassium chloride, sodium carbonate, calcium carbonate, sodium acid carbonate, copper sulfate crystal be dissolved in formed after water acid,
Alkali, salting liquid class electrolyte.
Flexible cathodes support substrate is coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect preservative paper, sensing paper, dress
Adorn paper, pouncing paper, plastics, cloth, malthoid and one kind in glass cloth or on surface apply eutectic by a kind of in these materials
The film that point metallic ink is supported.
Contain 0.01wt%~80wt% conductive nanoparticles in conducting metal ink, electrolyte solution；The conduction
Property nano particle be particle diameter 1nm~900nm platinum, gold, silver, copper, iron, aluminium, antimony, bismuth, cadmium, germanium, nickel, rhodium, tantalum, lead, tungsten, rhenium,
Constantan, tungsten-rhenium alloy or nickel-cadmium, CNT or graphene.
As shown in figure 1, the preparation method that the present invention also provides a kind of flexible electrochemical capacitor of printing-type, comprises the following steps：
S1：Determine flexible anode support substrate, Flexible cathodes support substrate；
S2：The low melting point liquid metal ink is coated on anode support base surface by printing equipment, sun is formed
Pole；
S3：Anode surface is sprayed water, water membrane is formed, is attached on this moisture film by a kind of sheet metal in gold, silver, copper
Negative electrode is served as, power supply is connected between this anode and negative electrode afterwards, cell reaction then occurs in moisture film, is produced at its Anodic
The low-melting-point metal film oxidation of anode surface is consequently formed a thin layer insulating barrier, serves as dielectric by raw oxygen；Move afterwards
Walk sheet metal negative electrode；
S4：In insulating barrier dielectric surface spray solution class electrolyte, the negative electrode of electrochemical capacitor is used as；
S5：Flexible cathodes support substrate is attached on electrolyte solution surface, is applied on the Flexible cathodes support substrate surface
Low-melting-point metal ink is applied, afterwards the structure being encapsulated between anode support base, cathode support substrate is compressed using fixture
It is fixed, and avoid solution from evaporating end encapsulation using silica gel, that is, form electrochemical capacitor；
S6：Repeat the above steps, form multilayer electrochemical capacitor.
Embodiment 1：
It is the flexible electrolytic capacitor structural representation of printing-type of the embodiment of the present invention 1 shown in Fig. 2.It is soft in the present embodiment
Property anode support base 1 from 5cm*5cm*0.05mm coated paper, will contain 0.25wt% gallium oxides in this substrate
Liquid gallium conducting metal ink prints painting and is covered with the form of a film, the conductive film 2 that thickness is 0.1mm is formed, in this electrode
Drawn with regular copper lines and be used as follow-up capacitor anode terminals 3 in film end.In the above-mentioned surface sprinkling of film 2, one layer is formed
Thickness about 1mm moisture film, attaches copper metal piece as negative electrode on this moisture film, now, electricity is connected between the anode and cathode
Source, then occurs cell reaction in moisture film, and the oxygen produced wherein at gallium thin film positive pole is by the shallow-layer surface of anode gallium film
Partial oxidation, is consequently formed a thin layer gallium oxide insulating barrier 4, serves as the dielectric of electrochemical capacitor, metal copper sheet is removed afterwards, in
It is that gallium oxide insulating barrier 4 i.e. direction is extraneous.Now, 5cm*5cm*0.05mm coated paper is attached on the surface of insulating barrier dielectric 4
5, spray concentration is 10wt% NaCl aqueous electrolytes on paper, after it permeates paper 5, then in paper exterior face surface
Printing applies and applies the liquid gallium low-melting-point metal ink containing 0.25wt% gallium oxides, forms the conductive thin that thickness is 0.1mm
Film 6, is drawn with regular copper lines in this film end and is used as follow-up capacitance cathode terminals 7.Thus flexible electrolysis electricity is just completed
The making of appearance.This electric capacity is charged in use, once terminals 3,7 connect power supply positive and negative electrode respectively, you can realize to electric capacity
Quick charge；During to electronics, respectively by terminals 3,7 connection of electronic devices two ends, then power supply can be achieved.
Note：
Moisture film is intended only as middle processing link and used, and evaporates afterwards, therefore not shown in figure.
Copper metal piece is used as middle processing link, not shown in figure.
Embodiment 2：
It is the plane formula multilayer electrolytic capacitor structure schematic diagram of the embodiment of the present invention 2 shown in Fig. 3.The present embodiment is folded for plane
Layer electrochemical capacitor, more than 2 electrochemical capacitors being made in embodiment 1, which are stacked, to be formed, and thus reaches bigger storing up electricity
Density.6 layers of electrochemical capacitor, respectively 11,22,33,44,55,66 are had in Fig. 3.Each of which layer electrolytic capacitor structure and system
Make method completely in the same manner as in Example 1.
Embodiment 3：
Fig. 4 is the column formula multilayer electrolytic capacitor structure schematic diagram of the embodiment of the present invention 3, and it is in concentric annular structure to have 6 layers
Electrochemical capacitor, respectively 11,22,33,44,55,66.Each of which layer electrolytic capacitor structure is in cylinder, structure and shape
There is difference with foregoing, be primarily to facilitate some applications or moulding demand, but preparation method completely with phase in embodiment 1
Together.
Embodiment of above is merely to illustrate the present invention, rather than limitation of the present invention.Although with reference to embodiment to this hair
It is bright to be described in detail, it will be understood by those within the art that, to technical scheme carry out it is various combination,
Modification or equivalent substitution, without departure from the spirit and scope of technical solution of the present invention, the right that all should cover in the present invention is wanted
Ask among scope.
Claims (7)
1. the flexible electrochemical capacitor of a kind of printing-type, it is characterised in that the flexible electrochemical capacitor of the printing-type includes：Flexible anode branch
Support group bottom, anode, insulating barrier dielectric, the electrolyte for serving as negative electrode and Flexible cathodes support substrate；The insulating barrier dielectric
For the insulating barrier dielectric formed after being aoxidized to anode by electrolysis process；
Wherein, the flexible anode support substrate is coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect preservative paper, sensing
One kind in paper, facing paper, pouncing paper, plastics, cloth, malthoid and glass cloth；
The anode is to be coated in the film being made on anode support base by low melting point liquid metal ink；
The insulating barrier dielectric is to be powered after being sprayed water to the anode after impressed cathodic, by cell reaction technique that anode is golden
The insulating barrier thin dielectric film formed after the superficial oxidation of category film.
2. the flexible electrochemical capacitor of printing-type according to claim 1, it is characterised in that the low melting point liquid metal ink
Be pure gallium or in containing indium, tin, mercury, sodium, potassium, caesium, lead, bismuth, copper, aluminium and chromium it is a kind of, be dissolved in gallium two or three
The low temperature multicomponent alloy of middle formation；The quality proportioning of gallium is 50%~99% in the alloy；Remaining gold added in gallium
Belong to for two or three when, remaining described intermetallic quality proportioning be any collocation.
3. the flexible electrochemical capacitor of printing-type according to claim 1 or 2, it is characterised in that the electrolysis for serving as negative electrode
Matter is to be close to the solution class electrolyte of the insulating barrier thin dielectric film.
4. the flexible electrochemical capacitor of printing-type according to claim 3, it is characterised in that the electrolyte for serving as negative electrode
For：Carbonic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, barium hydroxide, one hydration ammonia, Kocide SD, sodium chloride, potassium chloride, sodium carbonate,
A kind of in calcium carbonate, sodium acid carbonate, copper sulfate crystal is dissolved in the acid formed after water, alkali, salting liquid class electrolyte.
5. the flexible electrochemical capacitor of printing-type according to claim 4, it is characterised in that the Flexible cathodes support substrate is
Coated paper, moistureproof paper, light proof paper, waterproof paper, insulating paper, insect preservative paper, sensing paper, facing paper, pouncing paper, plastics, cloth, malthoid
With one kind in glass cloth；Or by a kind of Flexible cathodes support substrate constituted in these materials on the surface away from anode
Apply the film that low-melting-point metal ink is supported.
6. the flexible electrochemical capacitor of printing-type according to claim 5, it is characterised in that low-melting-point metal ink or electrolyte
Contain 0.01wt%~80wt% conductive nanoparticles in solution；The conductive nanoparticle is particle diameter 1nm~900nm's
Platinum, gold, silver, copper, iron, aluminium, antimony, bismuth, cadmium, germanium, nickel, rhodium, tantalum, lead, tungsten, rhenium, constantan, tungsten-rhenium alloy, nickel-cadmium, carbon nanometer
Pipe or graphene.
7. a kind of method of the flexible electrochemical capacitor of printing-type for making described in any one of claim 1~6, methods described be divided into as
Lower step：
Determine flexible anode support substrate and Flexible cathodes support substrate；
The low melting point liquid metal ink is coated on anode support base surface by printing equipment, anode is formed；
Anode surface is sprayed water, water membrane is formed, attaches and served as by a kind of sheet metal in gold, silver, copper on the moisture film
Negative electrode；
Power supply is connected between the anode and negative electrode, cell reaction occurs in moisture film, the oxygen produced at its Anodic will
The low-melting-point metal film oxidation of anode surface, forms a thin layer insulating barrier, serves as dielectric；
Remove sheet metal negative electrode；
In insulating barrier dielectric surface spray solution class electrolyte, the negative electrode of electrochemical capacitor is used as；
Flexible cathodes support substrate is attached on electrolyte solution surface；
Low-melting-point metal ink is applied on the Flexible cathodes support substrate surface；
The structure being encapsulated between anode support base, cathode support substrate is fixed using fixture；
Avoid solution from evaporating end encapsulation using silica gel, that is, form electrochemical capacitor；
Repeat the above steps, form multilayer electrochemical capacitor.
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| CN105696420B (en) * | 2016-01-26 | 2017-06-16 | 云南科威液态金属谷研发有限公司 | A kind of conductive paper and preparation method thereof |
| CN106840226B (en) * | 2017-03-29 | 2019-09-20 | 南京大学 | Flexible wearable health sensor and its preparation and measurement method based on micro optical fiber structure |
| CN107267832B (en) * | 2017-06-13 | 2019-03-22 | 清华大学 | A kind of porous liquid metal material of temperature control irreversible transition and its preparation and application |
| CN107196550A (en) * | 2017-07-11 | 2017-09-22 | 清华大学 | A kind of printable energy capture device |
| CN109428104B (en) * | 2017-08-31 | 2021-07-20 | 中国科学院理化技术研究所 | Liquid metal biomass battery |
| CN109273169B (en) * | 2018-09-18 | 2020-01-07 | 北京梦之墨科技有限公司 | Gallium-based transparent conductive film, preparation method thereof and electronic device |
| WO2020062223A1 (en) * | 2018-09-30 | 2020-04-02 | 哈尔滨工业大学（深圳） | One-stop supercapacitor and preparation method therefor |
| CN110854013B (en) * | 2019-11-11 | 2022-07-26 | 中国科学院金属研究所 | Large-area continuous ultrathin two-dimensional Ga 2 O 3 Preparation method and application of amorphous film |
| CN114271828B (en) * | 2021-12-22 | 2023-08-29 | 香港城市大学成都研究院 | Degradable high-array flexible device for brain-computer interface and preparation method thereof |
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| CN101351857A (en) * | 2005-12-28 | 2009-01-21 | 昭和电工株式会社 | Capacitor and method for manufacturing same |
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