CN104916456B - A kind of high-energy density super capacitor and preparation method thereof - Google Patents
A kind of high-energy density super capacitor and preparation method thereof Download PDFInfo
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- CN104916456B CN104916456B CN201410088296.7A CN201410088296A CN104916456B CN 104916456 B CN104916456 B CN 104916456B CN 201410088296 A CN201410088296 A CN 201410088296A CN 104916456 B CN104916456 B CN 104916456B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000007772 electrode material Substances 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 230000005611 electricity Effects 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- -1 tetrafluoroborate Chemical compound 0.000 claims description 6
- 238000007781 pre-processing Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000002322 conducting polymer Substances 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical group O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 125000006091 1,3-dioxolane group Chemical class 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003026 Acene Polymers 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 239000011883 electrode binding agent Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- 238000001994 activation Methods 0.000 abstract description 7
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 description 15
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002109 single walled nanotube Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses a kind of high-energy density super capacitors and preparation method thereof, belong to electrochemical energy storage field.By introducing metal lithium electrode in ultracapacitor assembling process come coordination electrode material electrochemical state, reach charge injecting electrode material, so as to obtain the positive and negative pole material of electrochemical potentials adjustment, so that the operating potential window of positive and negative electrode is optimized in ultracapacitor, the operating voltage and specific capacity for realizing device are promoted simultaneously, so as to improve super capacitor energy density.The electrochemical activation process that can be carried out by metal lithium electrode capacitor produced simultaneously makes it have overlength cycle life come stable potential window.The present invention is simple and compatible with prior art with technical process, and for improving device performance significant effect, therefore with great application prospect.
Description
Technical field
The present invention relates to the supercapacitor technologies fields for electrochemical energy storage, and in particular to a kind of high-energy is close
Spend ultracapacitor and preparation method thereof.
Background technology
Ultracapacitor is also known as electrochemical capacitor, by the electric double layer ionic adsorption or redox reaction of electrode surface
Charge is stored, performance is between physical capacitor and secondary cell.Ultracapacitor not only possesses far above physical capacitors
The energy density of device, in the several seconds just achievable charge/discharge rates, can high-power/current charging and discharging, cycle life up to ten thousand time,
Close to absolutely efficiency for charge-discharge, can be used in extreme high and low temperature environment（- 40~70 DEG C）And it is safe can be long-term
The characteristics such as non-maintaining are also that secondary cell is incomparable.These superior performances, make ultracapacitor be expected to consumer electronics,
It is used widely in the fields such as electric vehicle, intelligent grid, energy electricity generation system, aerospace and military affairs.But super capacitor
The extensive use of device is still limited by its relatively low energy density, how under the premise of ultracapacitor advantage is kept, into one
Step improves its energy density, and the level being allowed to close to secondary cell is current urgent problem to be solved.
The energy density E and specific capacitance C of ultracapacitor and operating voltage U's is square directly proportional：E=1/2CU2, therefore,
The raising of super capacitor energy density can be realized by improving specific capacitance or operating voltage.The specific capacitance of ultracapacitor depends on
In electrode material, therefore main research work at present all concentrates on and obtains high performance electrode material.The other direction of research is
The electrolyte of high voltage window is developed to improve the operating voltage of ultracapacitor, can be made using il electrolyte at present
The operating voltage of ultracapacitor is increased to more than 3.5V.
Research achieves greater advance in terms of electrode material and electrolyte, however, common problem is, by electrode material
After material and electrolyte are assembled into device, the voltage available window of electrolyte and the height ratio capacity of electrode material are underused.Cause
It, can not be under the potential window of optimization for after ultracapacitor is assembled into, the potential window of positive and negative electrode material is restricted
Work.The specific capacitance of electrode material is also influenced by the operating potential window of electrode, particularly metal oxide, conducting polymer
For the fake capacitance electrode material for storing charge with Reversible redox reaction with the Carbon Materials containing functional group, different potentials window
The specific capacitance difference of mouth lower electrode material is very big, and when electrode material is after device is formed, operating potential window often only has three
The half of potential window during electrode test, therefore the chemical property of electrode material can not play completely, lead to device specific capacitance
Very big reduction.
In order to solve material height ratio capacity and electrolyte voltage available window is assembled into asking of cannot being made full use of after device
Topic, currently employed two methods：Quality matches and asymmetric capacitor.By the quality matches of positive and negative electrode material, ensure it
In a pole material it is extremely excessive relative to other one, with meet positive and negative anodes can reach simultaneously electrolyte voltage available window up and down
Limit.However quality matches can only improve the operating voltage of ultracapacitor, and the specific capacity of ultracapacitor can not be increased.It is not right
Claim capacitor, be the super electricity assembled using Different Pore Structures Carbon Materials or different types of electrode material respectively as positive and negative anodes
Container by the use of the Carbon Materials of different pore size size as positive and negative anodes to match adsorbed zwitterion, reaches increase specific capacitance,
It, could be to meeting positive and negative pole material by needing to carry out a large amount of experiment so as to increase the energy density purpose of ultracapacitor
Pore structure material matches to realize.Asymmetric capacitor based on different energy storage mechnisms, however it remains in positive and negative anodes Performance Match
Problem, the device in addition assembled is in the performances such as cycle life and high current charge-discharge by the material electrodes that fake capacitance reaction occurs
It is affected, gap is clearly compared with charcoal base symmetry type capacitance device.Only positive and negative electrode capacity is identical, and operating voltage again can
In the case of reaching electrolyte maximum voltage available window, the energy density of ultracapacitor can just reach very big.We are accordingly
Related notion is proposed, is adjusted respectively by the operating potential window to positive and negative electrode, realizes that super capacitor energy is close
The maximization of degree（Referring to applying for a patent 201310093023.7）.But how simplifying phase relevant design and developing has practical value
Ultracapacitor device still needs further research.
Invention content
The purpose of the present invention is to provide a kind of high-energy density super capacitors and preparation method thereof, pass through redesign
Supercapacitor structures change electrode material electrode condition new method to realize, increase metal lithium electrode wherein so as to super
The initial electrochemical potentials of capacitor positive and negative electrode electrode material are regulated and controled, and can realize the usage in ultracapacitor
Current potential adjustment is carried out in the process.The present invention is on the basis of conventional ultracapacitor production technology, is located in advance by electrochemistry
Reason process allows the ultracapacitor being assembled into work under optimal potential window, realize device operating voltage and
The promotion of specific capacity, so as to greatly improve the energy density of capacitor devices.
Technical solution of the present invention is as follows：
A kind of preparation method of high-energy density super capacitor, this method first press positive electrode, negative electrode and diaphragm
More solito capacitor technique is assembled, and is aided with metal lithium electrode, the super electricity of three-electrode system is assembled into after injection electrolyte
Container；Then it is realized by preprocessing process and charge is injected separately into positive and negative electrode, make the initial electrochemical potentials of positive and negative electrode
With time modulation to specific potential（That is E ' ov）, so as to prepare high-energy density super capacitor.
It is described to realize that the process that charge is injected separately into positive and negative electrode is by preprocessing process：
Anode and cathode can be used in maximum voltage section with identical current value relative to lithium electrode in electrolyte simultaneously
Constant current charge-discharge test is carried out respectively, obtains the intersection point E ' ov of anode constant-current discharge curve and cathode constant-current charge curve, finally
Positive and negative electrode is used to constant current or constant pressure charge and discharge simultaneously to E ' ov.
This method makes positive and negative electrode in the ultracapacitor being finally assembling to sharp to greatest extent during later stage usage
With the available maximum voltage section of electrolyte.Corresponding different electrode material and electrolyte can use same method to carry out
Regulation and control.
Prepared high-energy density super capacitor can carry out electrochemistry work during usage by metal lithium electrode
Change, make it have overlength cycle life, detailed process is：The positive and negative electrode of ultracapacitor during usage is opposite respectively
It can be obtained just with constant current charge-discharge test is carried out respectively with identical current value in maximum voltage section in electrolyte in lithium electrode
Intersection point the E ' ' ov of pole constant-current discharge curve and cathode constant-current charge curve.Finally by positive and negative electrode simultaneously using constant current or constant pressure
Charge and discharge obtain the positive and negative electrode after current potential modulation to E ' ' ov.It is used so as to fulfill its long circulating.
Electrode slice in the high-energy density super capacitor（Electrode）Be made as common process, i.e., by active electrode material
Material carries out dispensing, coating, tabletting and slice with binding agent and conductive agent and obtains.
The electrode material can be Carbon Materials（Such as activated carbon, template carbon, activated carbon fibre, carbon aerosol, carbon nanometer
Pipe, graphene, cracking charcoal, graphite etc.）, metal oxide（Such as ruthenium-oxide, manganese oxide, nickel oxide, vanadium oxide, tin oxide, oxidation
Cobalt, iron oxide etc.）Or metal hydroxide material（Nickel hydroxide, cobalt hydroxide, iron hydroxide etc.）And conducting polymer materials
（Polypyrrole, polyaniline, gathers to benzene, polyacene etc. polythiophene）One or more of composite material（Such as ruthenium-oxide/graphite
Alkene, Polymerization of Polyaniline/carbon Nanotube, polyaniline/manganese oxide etc., polypyrrole/manganese oxide/graphene etc.）.
The electrolyte can be aqueous electrolyte（Such as aqueous sulfuric acid, potassium hydroxide aqueous solution and lithium salts, sylvite, sodium
Neutral aqueous solution of salt etc.）, organic electrolyte（Such as perchlorate, tetrafluoroborate, hexafluorophosphate or trifluoromethyl sulfonic acid
Deng solution in organic solvent）Or various ionic liquids etc.；The organic solvent is propylene carbonate, ethylene carbonate, carbon
Acid propylene ester, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, sulfolane, second
One or more of nitrile, 1,3- dioxolanes, 1,2- dimethoxy-ethanes and 1,4- butyrolactone etc..
It advantages of the present invention and has the beneficial effect that：
1st, the design of ultracapacitor of the present invention is formed in addition to the positive and negative electrode material of general ultracapacitor is fabricated to just
Negative electricity pole piece outside electrolyte, increases a metal lithium electrode, forms the ultracapacitor of three-electrode system；Then pass through
Preprocessing process, which is realized, by charge is injected separately into positive and negative electrode, makes the initial electrochemical potentials of positive and negative electrode with time modulation to specific
Current potential（That is E ' ov）, so as to fulfill being greatly improved for device energy density.
Compared to the method for realizing super capacitor energy very dense before（Chinese invention patent
201310093023.7）, it is of the invention using completely new electrochemical potentials regulation and control method, greatly simplify operating process.Using
Three-electrode system designs, completely compatible with existing packaging technology, can obtain with practical value ultracapacitor device.Institute simultaneously
Capacitor can carry out electrochemical activation process come stable potential window during usage by metal lithium electrode, make its tool
There is overlength cycle life.
2nd, the method proposed by the present invention for realizing high-energy density super capacitor has general applicability.It is of the invention direct
Using the operating potential window for the method optimizing positive and negative electrode that the electrochemical potentials to positive and negative electrode are regulated and controled, therefore it is from root
The voltage available window of the specific capacity of electrode material and electrolyte in existing ultracapacitor is solved on source to be fully utilized
The problem of, suitable for any electrolyte system and any electrode material.
3rd, the method proposed by the present invention for realizing high-energy density super capacitor, can give full play to electrode material and electricity
The performance of liquid is solved, the specific capacity and operating voltage of ultracapacitor can be improved simultaneously, thus can be increased substantially existing super
The energy density of capacitor expands the application field of ultracapacitor.
4th, present invention does not require positive and negative electrodes to exactly match（Identical in quality, specific capacity is identical）, the scope of application is more extensive.
5th, the method proposed by the present invention for realizing super capacitor energy very dense is simple for process, and different batches can weigh
Renaturation is strong, is easy to amplify production on a large scale.
6th, the present invention introduces lithium electrode in ultracapacitor can effectively solve the lithium source and coulombic efficiency of electrode material
Problem, that has greatly widened electrode material can application range.
7th, ultracapacitor device design proposed by the present invention, has high practical value.
8th, ultracapacitor device design proposed by the present invention, can realize and be carried out during the usage of ultracapacitor
Current potential adjusts, and makes it have overlength cycle life.
Description of the drawings
Fig. 1 is the comparison of typical ultracapacitor and the technological process of production of the present invention；In figure：（a）For conventional super capacitance
Device technological process；（b）For present invention process flow.
Fig. 2 is the assemble method of ultracapacitor device of the present invention and modulation principle schematic；In figure：(a) it is the present invention
The assemble method schematic diagram of ultracapacitor device；（b）For principle schematic diagram of the present invention（The height of dash area represents just in figure
The electrode potential of cathode, E0v,E0v' be respectively positive and negative anodes initial electrochemical potentials and modulation after positive and negative anodes electrochemistry electricity
Position）.
Fig. 3 is the specific regulation and control method schematic diagram of ultracapacitor device of the present invention.
Fig. 4 is by the front and rear electrification of ultracapacitor formed of electric potential regulating of Graphene electrodes in the embodiment of the present invention 1
Learn performance comparison.
Fig. 5 by Graphene electrodes in the embodiment of the present invention 1 the front and rear ultracapacitor formed of electric potential regulating and follow
Chemical property comparison is re-activated after ring.
Fig. 6 is by the front and rear ultracapacitor formed of electric potential regulating of multi-walled carbon nanotube electrode in the embodiment of the present invention 2
Chemical property comparison.
Fig. 7 is by the front and rear ultracapacitor formed of electric potential regulating of single pipe electrode in the embodiment of the present invention 3
Chemical property comparison.
Fig. 8 is the work(of ultracapacitor that each electrode material is assembled into before and after current potential modulation in 1-3 of the embodiment of the present invention
Rate-energy density profile.
Specific embodiment
The present invention is illustrated with reference to embodiment：
Shown in conventional ultracapacitor production technology such as Fig. 1 (a), the present invention is in conventional ultracapacitor production technology
On the basis of introduce lithium electrode increase the step of regulating and controlling to the initial electrochemical potentials of electrode material simultaneously, make what is be assembled into
Positive and negative electrode can work under optimal potential window in ultracapacitor, can promote the operating voltage and ratio of device simultaneously
Capacity, so as to the device energy density that maximized, as shown in Fig. 2 (a)-(b).
The step of initial electrochemical potentials are regulated and controled（Charge injects positive and negative electrode process）In ultracapacitor device group
It is carried out after dress（Such as Fig. 1 (b)）.
Embodiment 1
Regulation and control are using graphene as electrode material（Oxygen content 6.5at%, specific surface area 412m2/g）With with LiPF6Carbonic acid second
Enester/dimethyl carbonate solution is as follows for the process of the super capacitor system of electrolyte：
Grapheme material is made into electrode slice, with LiPF6Ethylene carbonate/dimethyl carbonate solution as electrolyte
（Wherein LiPF6The volume ratio of a concentration of 1mol/L, ethylene carbonate and dimethyl carbonate is 1:1）, while as positive and negative anodes and
Lithium foil electrode is assembled into ultracapacitor device.The available potential window upper limit 4.3V and the 0.001V vs.Li of electrolyte it
Between so that positive and negative electrode is respectively relative to lithium electrode and carries out 20 cycles of constant current charge-discharge with 175mA/g current densities.It obtains just
Intersection point E ' the ov of electrode discharge curve and negative electrode charging curve.Then positive and negative anodes are filled simultaneously（It puts）Electricity is to E ' ov constant pressures 12h.
The ultracapacitor device after modulation is obtained, as shown in Figure 3.
Such as Fig. 4 (a), for the graphene ultracapacitor before and after electric potential regulating, the device under 875mA/g current density conditions is electric
Pressure and specific capacity comparison, wherein device represents that device is represented with TGSC after regulation and control with GSC before regulation and control.As it can be seen that after electric potential regulating
Ultracapacitor device voltage and device specific capacity be all greatly increased.It is the stone after electric potential regulating such as Fig. 4 (b)
Cycle performance test of the black alkene device under 875mA/g current density conditions.As it can be seen that the ultracapacitor after electric potential regulating is protected
Hold good cyclical stability.
It, can if Fig. 5 (a) is the chemical property comparison after regulating and controlling during ultracapacitor usage before and after electrochemical activation
See, under 875mA/g current density conditions, the graphene ultracapacitor after electrochemical activation（TGSCreactivation）It can
To regain and the comparable specific capacities of TGSC.By electrochemical activation, so as to obtain the cycle life of overlength.
Before and after such as Fig. 5 (b) being the ultracapacitor and electrochemical activation under different current densities before and after current potential modulation
The comparison of high rate performance, it is seen then that graphene can give play to higher energy-storage property in the ultracapacitor after current potential modulation.
Simultaneously as it can be seen that good energy storage can be regained by carrying out electrochemical activation during usage to the ultracapacitor after modulation
Performance.
Embodiment 2
By multi-walled carbon nanotube（Diameter<2nm, 5-15 μm of length, specific surface area 500-700m2/ g, oxygen content 4.5at%）
Electrode slice is fabricated to, with LiPF6Ethylene carbonate/dimethyl carbonate solution as electrolyte（Wherein LiPF6A concentration of 1mol/
The volume ratio of L, ethylene carbonate and dimethyl carbonate is 1:1）, while it is assembled into super capacitor as positive and negative anodes and lithium foil electrode
Device device.Between the available potential window upper limit 4.3V and the 0.001V vs.Li of electrolyte so that positive and negative electrode is opposite respectively
20 cycles of constant current charge-discharge are carried out with 175mA/g current densities in lithium electrode.It obtains positive electrode discharge curve and negative electrode fills
Intersection point E ' the ov of electric curve.Positive and negative anodes are filled simultaneously afterwards（It puts）Electricity is to E ' ov constant pressures 12h.Obtain the ultracapacitor device after modulation
Part.
If Fig. 6 (a) is constant current charge and discharge of the multi-walled carbon nanotube ultracapacitor under different multiplying after electric potential regulating
Electric curve, it is seen then that the multi-walled carbon nanotube ultracapacitor after current potential modulation can be very stable under different current densities
Work.
Such as capacitances of the Fig. 6 (b) for multi-walled carbon nanotube in the ultracapacitor before and after current potential modulation under different current densities
The comparison of high rate performance, it is seen then that multi-walled carbon nanotube can give play to higher storage in the ultracapacitor after current potential modulation
It can performance.
Embodiment 3
By single-walled carbon nanotube（Diameter<10nm, 5-15 μm of length, specific surface area 250-300m2/ g, oxygen content 6.5at%）
Electrode slice is fabricated to, with LiPF6Ethylene carbonate/dimethyl carbonate solution as electrolyte（Wherein LiPF6A concentration of 1mol/
The volume ratio of L, ethylene carbonate and dimethyl carbonate is 1:1）, while it is assembled into super capacitor as positive and negative anodes and lithium foil electrode
Device device.Between the available potential window upper limit 4.3V and the 0.001V vs.Li of electrolyte so that positive and negative electrode is opposite respectively
20 cycles of constant current charge-discharge are carried out with 175mA/g current densities in lithium electrode.It obtains positive electrode discharge curve and negative electrode fills
Intersection point E ' the ov of electric curve.Positive and negative anodes are filled simultaneously afterwards（It puts）Electricity is to E ' ov constant pressures 12h.Obtain the ultracapacitor device after modulation
Part.
If Fig. 7 (a) is constant current charge and discharge of the single-walled carbon nanotube ultracapacitor under different multiplying after electric potential regulating
Electric curve, it is seen then that the single-walled carbon nanotube ultracapacitor after current potential modulation can be very stable under different current densities
Work.
Such as capacitances of the Fig. 7 (b) for single-walled carbon nanotube in the ultracapacitor before and after current potential modulation under different current densities
The comparison of high rate performance, it is seen then that single-walled carbon nanotube can give play to higher storage in the ultracapacitor after current potential modulation
It can performance.
The ultracapacitor that various electrode materials are assembled into before and after current potential modulation in above-described embodiment is given such as Fig. 8
Power-energy density profile.The result shows that after electrode potential modulation, super capacitor energy density has significant increase,
Maintain the high power characteristic of ultracapacitor.
Claims (6)
1. a kind of preparation method of high-energy density super capacitor, it is characterised in that：This method is first by positive electrode, negative electrode
It is assembled with diaphragm, is aided with metal lithium electrode, the ultracapacitor of three-electrode system is assembled into after injection electrolyte；Then lead to
It crosses preprocessing process realization and charge is injected separately into positive and negative electrode, make the initial electrochemical potentials of positive and negative electrode with time modulation to spy
Current potential is determined, so as to prepare high-energy density super capacitor；Charge is injected separately into just by described realized by preprocessing process
Negative electrode, the initial electrochemical potentials for making positive and negative electrode are with the detailed process of time modulation to specific potential：Dress up three electrode bodies
After the ultracapacitor of system, while anode and cathode can be used in maximum voltage section with identical relative to lithium electrode in electrolyte
Current value carry out constant current charge-discharge test respectively, obtain the intersection point E ' of anode constant-current discharge curve and cathode constant-current charge curve
Positive and negative electrode is finally used constant current or constant pressure charge and discharge to E ' ov by ov simultaneously.
2. the preparation method of high-energy density super capacitor according to claim 1, it is characterised in that：The high-energy
Electrode is made as common process in density ultracapacitor, i.e., matches active electrode material and binding agent and conductive agent
Material, coating, tabletting and slice obtain, and the electrode material is Carbon Materials, metal oxide, metal hydroxide material and conduction
The composite material of one or more of polymer material.
3. the preparation method of high-energy density super capacitor according to claim 2, it is characterised in that：The Carbon Materials
For activated carbon, template carbon, activated carbon fibre, carbon aerosol, carbon nanotube, graphene, cracking charcoal or graphite；The metal oxidation
Object is ruthenium-oxide, manganese oxide, nickel oxide, vanadium oxide, tin oxide, cobalt oxide or iron oxide；The metal hydroxide material is
Nickel hydroxide, cobalt hydroxide or iron hydroxide；The conducting polymer materials are polypyrrole, polythiophene, polyaniline, it is poly- to benzene or
Polyacene.
4. the preparation method of high-energy density super capacitor according to claim 1, it is characterised in that：The electrolyte
For aqueous electrolyte, organic electrolyte or various ionic liquids；The aqueous electrolyte is aqueous sulfuric acid, potassium hydroxide is water-soluble
Liquid or lithium salts, sylvite, sodium salt neutral aqueous solution；The organic electrolyte is perchlorate, tetrafluoroborate, hexafluorophosphoric acid
The solution of salt or trifluoromethyl sulfonic acid in organic solvent, the organic solvent is propylene carbonate, ethylene carbonate, carbonic acid
Acrylic ester, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, sulfolane, acetonitrile,
One or more of 1,3- dioxolanes, 1,2- dimethoxy-ethanes and 1,4- butyrolactone.
5. a kind of high-energy density super capacitor prepared using claim 1 the method.
6. high-energy density super capacitor according to claim 5, it is characterised in that：The super electricity of high-energy density
Container can carry out electrochemical activation during usage by metal lithium electrode, and to ensure its cycle life, detailed process is：It will
The positive and negative electrode of ultracapacitor during usage be respectively relative to lithium electrode electrolyte can use maximum voltage section in
Identical current value carries out constant current charge-discharge test respectively, obtains the friendship of anode constant-current discharge curve and cathode constant-current charge curve
Point E " ov；Positive and negative electrode is finally obtained into the positive and negative electrode after current potential modulation simultaneously using constant current or constant pressure charge and discharge to E " ov,
So as to fulfill its long circulating performance.
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| CN105957725A (en) * | 2016-06-24 | 2016-09-21 | 安徽江威精密制造有限公司 | Composite electrode material added with bamboo charcoal and nickel aluminum hydrotalcite composite material and preparation method of composite electrode material |
| CN106981686B (en) * | 2017-04-12 | 2019-03-19 | 中国科学院金属研究所 | A kind of secondary cell using identical positive and negative anodes active material |
| CN109239157A (en) * | 2018-09-07 | 2019-01-18 | 常州大学 | A kind of non-enzyme sensor of graphene-NiO- polyaniline |
| CN112992555A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Electrode with residual ions, preparation and application |
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| CN101140829A (en) * | 2006-09-04 | 2008-03-12 | 富士重工业株式会社 | Lithium-ion capacitor |
| CN103413692A (en) * | 2013-08-25 | 2013-11-27 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor positive plate and lithium ion capacitor using same |
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| CN101140829A (en) * | 2006-09-04 | 2008-03-12 | 富士重工业株式会社 | Lithium-ion capacitor |
| CN103413692A (en) * | 2013-08-25 | 2013-11-27 | 中国科学院青岛生物能源与过程研究所 | Lithium ion capacitor positive plate and lithium ion capacitor using same |
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