CN101494123A - Mixed electrochemical capacitor - Google Patents
Mixed electrochemical capacitor Download PDFInfo
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- CN101494123A CN101494123A CN 200910037614 CN200910037614A CN101494123A CN 101494123 A CN101494123 A CN 101494123A CN 200910037614 CN200910037614 CN 200910037614 CN 200910037614 A CN200910037614 A CN 200910037614A CN 101494123 A CN101494123 A CN 101494123A
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- carbonate
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a hybrid electrochemical capacitor which consists of a positive electrode, a negative electrode, a membrane barrier between the positive electrode and the negative electrode, and electrolytic solution. The active material of the negative electrode adopts an active carbon material. The hybrid electrochemical capacitor is characterized in that the active material of the positive electrode adopts a mixture or a complex of an iron-based lithium inserted compound, a vanadium-based lithium inserted compound or a Ni-Mn-Co lithium inserted compound and active carbon; the electrolytic solution is a lithium salt solution containing supporting electrolyte. The positive electrode of the hybrid electrochemical capacitor is a double-layer mechanism with a lithium ion battery and a double electric layer capacitor so as to greatly improve the discharge performance at high rate; and the supporting electrolyte is added into the electrolytic solution for greatly increasing the salt concentration and the ionic conductivity , thus solving the problems of lacking body electrolytic solution when the double electric layers are formed and high requirements of the electrical conductivity during the discharging at high rate.
Description
Technical field
The present invention relates to a kind of electrochemical capacitor, relate in particular to a kind of hybrid electrochemical capacitor.
Background technology
Double electric layer capacitor forms electric double layer savings electric charge by electrode material and electrolyte interface, material is general to use active carbon with high specific surface area with electric double layer capacitance characteristic, charcoal fiber, charcoal-aero gel, carbon nano-tube etc., on the cycle life 100,000 times, can fast charging and discharging.But there is following shortcoming in it: (1) capacity density is low, improve capacity density often by increasing the specific surface of material, material surface is done modification processing etc., and the capacity of these methods raising double electric layer capacitors is very limited, and the increase of specific surface has reduced the conductivity of material; Forming electric double layer when (2) charging has caused the poorness of bulk electrolysis liquid to increase the solution internal resistance; (3) influenced by electrolyte decomposition voltage and raw material of wood-charcoal material and electrolyte compatibility, aqueous systems voltage generally has only 1.0V, organic system voltage 2.7V.At these problems, existing research improves its performance by following several respects: (1) substitutes with metal oxide or part substitutes the raw material of wood-charcoal material, raising is than electric capacity and operating voltage, but the only suitable at present aqueous systems of metal oxide, the organic system performance is very undesirable, and it is because costing an arm and a leg of noble metal limits its practical application with base metal cycle performance difference; (2) substitute or partly substitute the raw material of wood-charcoal material with conducting polymer, raising is than electric capacity and operating voltage, but the conducting polymer synthesis condition is harsh, and price height, cycle performance are also undesirable; (3) with embedding lithium type compound zero strain material Li particularly
4Ti
5O
12Do negative pole, the raw material of wood-charcoal material is done the anodal asymmetric mixed capacitor of forming, and has improved capacity density greatly.But said method does not all solve the poor problem of bulk electrolysis liquid that electric double layer causes.
Lithium ion battery energy density height, but its both positive and negative polarity is subjected to lithium ion migration restriction entirely by the doff lithium energy storage, its big high rate performance is not satisfactory, and cycle life is also far below double electric layer capacitor in addition.
Therefore, make a kind of energy storage device that can solve the above-mentioned shortcoming of double electric layer capacitor and lithium ion battery and have its advantage concurrently, paid close attention to by people.Application number is 200510110461.5, denomination of invention is the Chinese patent of " lithium ion battery material is as the non-aqueous system electrochemical mixed capacitor of positive pole ", it discloses a kind of non-aqueous system electrochemical mixed capacitor, the anodal high potential lithium ion insert material LiMn that adopts
2-xM
xO
4, negative pole adopts the porous active material, and electrolyte is the non-aqueous system that contains lithium ion; Application number is 200710017048.3, denomination of invention is the Chinese patent of " a kind of hybrid electrochemical capacitor and manufacture method thereof ", it discloses a kind of hybrid electrochemical capacitor and manufacture method thereof, the mixing of one or more of the transition metal oxide of anodal employing lithium, negative pole adopts the raw material of wood-charcoal material, and electrolyte adopts the non-water organic solution of lithium salts.Above-mentioned two pieces of described hybrid electrochemical capacitors of patent, positive electrode active materials all only adopt lithium ion to embed compound, the defective that crystal structure destroyed easily when it did not break away from the anode material for lithium-ion batteries high power discharge; Electrolyte all adopts the non-aqueous solution of lithium salts, is subjected to the influence of lithium salts solubility and degree of dissociation, and ionic conductivity has certain gap with the conductivity of double electric layer capacitor electrolyte generally below 10mS/cm.
Summary of the invention
Technical problem to be solved by this invention provides a kind of hybrid electrochemical capacitor, the defective that can avoid positive electrode active materials high power discharge structure to destroy easily, realize big multiplying power discharging, improve ionic conductivity, form and a kind ofly have lithium ion battery and double electric layer capacitor advantage concurrently and evade the energy storage device of its shortcoming.
The present invention solves the technical scheme that its technical problem adopts:
A kind of hybrid electrochemical capacitor, form by positive pole, negative pole, barrier film and electrolyte between both positive and negative polarity, the active material of described negative pole adopts absorbent charcoal material, it is characterized in that: it is that lithium intercalation compound, vanadium are that lithium intercalation compound or nickel manganese cobalt are the mixture or the compound of any and active carbon in the lithium intercalation compound that the active material of described positive pole adopts iron; Described electrolyte is the lithium salt solution that contains supporting electrolyte.
Described electrolyte is the aqueous solution, and its electrolyte is Li
2SO
4, LiNO
3, among LiCl or the LiOH one or more, concentration is that 0.5mol/L is to saturated solution concentration; Described supporting electrolyte is (NH
4)
2SO
4, Na
2SO
4, K
2SO
4, NH
4NO
3, NaNO
3, KNO
3, NH
4Among Cl, NaCl, KCl, NaOH, the KOH one or more.
Described electrolyte is non-water organic solution, and its electrolyte is LiPF
6, LiClO
4, LiBF
4, LiBOB, LiCF
3SO
3In one or more, solvent is a carbonic ester, concentration is that 0.5mol/L is to saturated solution concentration; Described supporting electrolyte is Et
4NBF
4, MeEt
3NBF
4, Me
2Et
2NBF
4, Et
4PBF
4, MeEt
3PBF
4, Me
2Et
2PBF
4, Et
4NPF
6, MeEt
3NPF
6Or Me
2Et
2NPF
6In one or more.
Described iron is that lithium intercalation compound is LiFePO
4, Li
2FeSiO
4Or one or more of its doping derivative products.
Described vanadium is that lithium intercalation compound is LiVPO
4F, Li
3V
2(PO
4)
3, LiV
3O
8, (Li) VOPO
4Or one or more of its doping derivative products;
Described nickel manganese cobalt is that lithium intercalation compound is LiNi
xMn
yCo
zO
2One or more of (wherein 0≤x, y, z≤1 and x+y+z=1) or its doping derivative products.
The mass percent η of active carbon satisfies 0＜η≤50% in the active material mixture of described positive pole or the compound.
Described carbonic ester is ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester at least two kinds.
Advantage of the present invention and the good effect that brings: hybrid electrochemical capacitor of the present invention, anodal active material employing lithium intercalation compound mixes or compound with active carbon, be lithium ion battery and the double-deck mechanism of double electric layer capacitor, improved the big multiplying power discharging property of material greatly; Add supporting electrolyte in the electrolyte, improved the concentration and the ionic conductivity of salt, the poor problem of bulk electrolysis liquid and big multiplying power discharging are to the demanding problem of conductivity when having solved the formation electric double layer.
Description of drawings
Fig. 1 is the charging and discharging curve of embodiment 1 under the 0.3A/g current density;
Fig. 2 is the charging and discharging curve of embodiment 2 under the 0.3A/g current density.
Embodiment
Below in conjunction with embodiment the present invention is described further, enforcement of the present invention includes but not limited to down routine execution mode.
Embodiment 1
With LiFePO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive and negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject the LiNO of 8mol/L
3Solution (adds 2mol/L KNO in addition
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, its charging and discharging curve as shown in Figure 1, as can be seen from Figure 1, charging and discharging curve is the double characteristic of electric double layer capacitance curve and lithium ion battery platform curve, and its operating voltage (about 1.5V) is higher than KOH aqueous systems double electric layer capacitor (1.0V).Discharge curve is less at the above slope of 1.0V, trends towards the discharge platform feature of lithium ion battery; Be lower than 1.0V lithium ion embedding lithium in lithium intercalation compound and finish, no longer possess the mechanism of lithium ion battery, embody the discharge characteristic of double electric layer capacitor.Because the conductivity of the aqueous solution more than non-water organic solution height, can satisfy the requirement of big multiplying power discharging fully, with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 85%.
Embodiment 2
With LiFePO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 4: 4: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiPF of 1mol/L
6/ ethylene carbonate+propene carbonate+methyl ethyl carbonate+dimethyl carbonate (adds 0.5mol/L Et in addition
4NBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, the charging and discharging curve of hybrid electrochemical capacitor as shown in Figure 2, as can be seen from Figure 2, charging and discharging curve also is the double characteristic of electric double layer capacitance curve and lithium ion battery platform curve.Discharge curve does not embed at this potential region lithium ion in the feature that 3.0～2.5V embodies double electric layer capacitor; Present the platform features of lithium ion battery at 2.5～1.8V, mainly embody embedding lithium mechanism; Finish 1.8V following lithium ion embeds, recover electric double layer mechanism.With 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 3
With LiCoO
2/ active carbon compound (quality of activated carbon content 25%), conductive agent acetylene black and adhesive PVDF mix by mass ratio at 8: 1: 1, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject the Li of 0.5mol/L
2SO
4Solution (adds 1mol/LNa in addition
2SO
4Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 86%.
Embodiment 4
With LiNi
0.3Mn
0.3Co
0.3Ti
0.1O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiPF of 1mol/L
6/ ethylene carbonate+propene carbonate+diethyl carbonate (adds 0.6mol/L MeEt in addition
3NBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 15mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 5
With LiV
3O
8Active carbon, conductive agent acetylene black and adhesive PVDF were by mass ratio 4: 4: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, with active carbon, acetylene black and PVDF are by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate, pack in the aluminum hull, inject the LiCl solution (add 1.5mol/L KCl in addition and do supporting electrolyte) of 3mol/L and do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 6
With LiVPO
4F/ active carbon compound (quality of activated carbon content 50%), conductive agent acetylene black and adhesive PVDF mix by mass ratio at 8: 1: 1, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiBF of 0.9mol/L
4/ ethylene carbonate+diethyl carbonate (adds 0.4mol/L Et in addition
4NPF
6Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 12mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 7
With Li
2FeSiO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject the LiNO of 5mol/L
3Solution (adds 2mol/L NH in addition
4NO
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 84%.
Embodiment 8
With Li
3V
2(PO
4)
3, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, the LiBOB/ ethylene carbonate+dimethyl carbonate that injects 0.7mol/L (adds 0.8mol/L Et in addition
4PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 81%.
Embodiment 9
With LiMnO
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 7: 1: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, the LiOH solution that injects 0.5mol/L (adds 2mol/L KNO in addition
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 10
With LiNi
0.5Mn
0.5O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiCF of 0.8mol/L
3SO
3/ ethylene carbonate+dimethyl carbonate (adds 0.6mol/LMeEt in addition
3NPF
6Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 13mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 83%.
Embodiment 11
With LiMn
0.8Co
0.2O
2/ active carbon compound (quality of activated carbon content 10%), conductive agent acetylene black and adhesive PVDF mix by mass ratio at 8: 1: 1, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiClO of 1mol/L
4/ ethylene carbonate+diethyl carbonate+propene carbonate (adds 0.6mol/L MeEt in addition
3PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 12
With LiFe
0.9Mg
0.1PO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiBF of 1.1mol/L
4/ ethylene carbonate+dimethyl carbonate+propene carbonate (adds 0.3mol/LMe in addition
2Et
2PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 13mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 13
With LiNi
0.3Mn
0.3Co
0.3Zn
0.1O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiPF of 1mol/L
6/ ethylene carbonate+methyl ethyl carbonate+diethyl carbonate (adds 0.3mol/LEt in addition
4NBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 13mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 14
With LiFe
0.95Zr
0.05PO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive and negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject the LiNO of 8mol/L
3Solution (adds 1mol/L NaNO in addition
3With 2mol/L KNO
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 15
With LiFe
0.92Al
0.08PO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 4: 4: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiPF of 1mol/L
6/ ethylene carbonate+propene carbonate+methyl ethyl carbonate+dimethyl carbonate (adds 0.2mol/L MeEt in addition
3NBF
4With 0.5mol/L Et
4NBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 15mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 81%.
Embodiment 16
With LiCo
0.8Ni
0.2O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject 0.5mol/L Li
2SO
4+ 2mol/L LiNO
3Solution (adds 1mol/L NaNO in addition
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 83%.
Embodiment 17
With LiNi
0.4Mn
0.4Co
0.2O
2/ active carbon compound (quality of activated carbon content 5%), conductive agent acetylene black and adhesive PVDF mix by mass ratio at 8: 1: 1, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject 0.8mol/LLiPF
6+ 0.2mol/L LiBF
4/ ethylene carbonate+propene carbonate+diethyl carbonate (adds 0.6mol/L MeEt in addition
3NBF
4With 0.2mol/L Et
4NPF
6Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 17mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 83%.
Embodiment 18
With LiV
3O
8Active carbon, conductive agent acetylene black and adhesive PVDF were by mass ratio 4: 4: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, with active carbon, acetylene black and PVDF are by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate, pack in the aluminum hull, inject the LiCl solution (add 1.5mol/LKCl in addition and 0.5mol/LNaCl does supporting electrolyte) of 3mol/L and do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 19
With LiV
0.9Ti
0.1PO
4F, active carbon, conductive agent acetylene black and adhesive PVDF were by mass ratio 7: 1: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject 0.9mol/L LiBF
4+ 0.2mol/L LiBOB/ ethylene carbonate+diethyl carbonate (adds 0.4mol/L Et in addition
4NPF
6+ 0.2mol/L MeEt
3NPF
6Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 20
With Li
2Fe
0.95Mg
0.05SiO
4, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, inject 5mol/L LiNO
3+ 1mol/L LiCl solution (adds 2mol/L NaNO in addition
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 21
With Li
3V
2(PO
4)
3, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject 0.7mol/L LiBOB+0.3mol/L LiPF
6/ ethylene carbonate+dimethyl carbonate (adds 0.4mol/L Et in addition
4PBF
4+ 0.2mol/L Me
2Et
2PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 22
With LiMn
0.9Co
0.1O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 7: 1: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, pack in the aluminum hull, the LiOH solution that injects 0.5mol/L (adds 2mol/L KNO in addition
3+ 1mol/L NaNO
3Do supporting electrolyte) do electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 82%.
Embodiment 23
With LiNi
0.45Mn
0.45Al
0.1O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 5: 3: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject 1mol/L LiCF
3SO
3+ 0.2mol/L LiPF
6/ ethylene carbonate+dimethyl carbonate (adds 0.6mol/L MeEt in addition
3NPF
6+ 0.2mol/L Me
2Et
2NPF
6Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 84%.
Embodiment 24
With LiNi
0.8Co
0.2O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 4: 4: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiClO of 1mol/L
4/ ethylene carbonate+diethyl carbonate+propene carbonate (adds 0.6mol/L MeEt in addition
3PBF
4+ 0.1mol/L Me
2Et
2PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 14mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 25
With LiFe
0.9Co
0.1PO
4/ active carbon compound (quality of activated carbon content 30%), conductive agent acetylene black and adhesive PVDF mix by mass ratio at 8: 1: 1, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject 0.8mol/L LiBF
4+ 0.2mol/L LiCF
3SO
3/ ethylene carbonate+dimethyl carbonate+propene carbonate (adds 0.3mol/L Me in addition
2Et
2PBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 13mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 80%.
Embodiment 26
With LiNi
0.4Mn
0.4Co
0.1Zn
0.1O
2, active carbon, conductive agent acetylene black and adhesive PVDF be by mass ratio 6: 2: 1: 1 mixes, adding an amount of NMP makees solvent and sizes mixing, evenly be coated on slurry on the aluminium foil with coating machine, 120 ℃ of oven dry, press mold becomes positive plate, and by making negative plate with sampling technology, folder is with diaphragm paper in the positive/negative plate with active carbon, acetylene black and PVDF, detest the aluminum hull of packing in the glove box that water is full of argon gas in anaerobism, inject the LiPF of 1mol/L
6/ ethylene carbonate+methyl ethyl carbonate+diethyl carbonate (adds 0.3mol/L Et in addition
4NBF
4+ 0.3mol/L MeEt
3NBF
4Do supporting electrolyte) electrolyte, encapsulation promptly gets hybrid electrochemical capacitor of the present invention.The conductivity that records electrolyte is 15mS/cm, and with 10A/g current density charge and discharge cycles 5000 times, capacitance keeps more than 84%.
Claims (8)
1. hybrid electrochemical capacitor, form by positive pole, negative pole, barrier film and electrolyte between both positive and negative polarity, the active material of described negative pole adopts absorbent charcoal material, it is characterized in that: it is that lithium intercalation compound, vanadium are that lithium intercalation compound or nickel manganese cobalt are the mixture or the compound of lithium intercalation compound and active carbon that the active material of described positive pole adopts iron; Described electrolyte is the lithium salt solution that contains supporting electrolyte.
2. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: described electrolyte is the aqueous solution, and its electrolyte is Li
2SO
4, LiNO
3, among LiCl or the LiOH one or more, concentration is that 0.5mol/L is to saturated solution concentration; Described supporting electrolyte is (NH
4)
2SO
4, Na
2SO
4, K
2SO
4, NH
4NO
3, NaNO
3, KNO
3, NH
4Among Cl, NaCl, KCl, NaOH, the KOH one or more.
3. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: described electrolyte is non-water organic solution, and its electrolyte is LiPF
6, LiClO
4, LiBF
4, LiBOB, LiCF
3SO
3In one or more, solvent is a carbonic ester, concentration is that 0.5mol/L is to saturated solution concentration; Described supporting electrolyte is Et
4NBF
4, MeEt
3NBF
4, Me
2Et
2NBF
4, Et
4PBF
4, MeEt
3PBF
4, Me
2Et
2PBF
4, Et
4NPF
6, MeEt
3NPF
6Or Me
2Et
2NPF
6In one or more.
4. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: described iron is that lithium intercalation compound is LiFePO
4, Li
2FeSiO
4Or one or more of its doping derivative products.
5. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: described vanadium is that lithium intercalation compound is LiVPO
4F, Li
3V
2(PO
4)
3, LiV
3O
8, (Li) VOPO
4Or one or more of its doping derivative products.
6. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: described nickel manganese cobalt is that lithium intercalation compound is LiNi
xMn
yCo
zO
2One or more of (wherein 0≤x, y, z≤1 and x+y+z=1) or its doping derivative products.
7. by the described hybrid electrochemical capacitor of claim 1, it is characterized in that: the mass percent η of active carbon satisfies 0＜η≤50% in the active material mixture of described positive pole or the compound.
8. by the described hybrid electrochemical capacitor of claim 3, it is characterized in that: described carbonic ester is ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester at least two kinds.
Priority Applications (1)
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|---|---|---|---|
| CN 200910037614 CN101494123A (en) | 2009-03-06 | 2009-03-06 | Mixed electrochemical capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910037614 CN101494123A (en) | 2009-03-06 | 2009-03-06 | Mixed electrochemical capacitor |
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Family
ID=40924656
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000386A (en) * | 2011-09-15 | 2013-03-27 | 海洋王照明科技股份有限公司 | Super hybrid capacitor and manufacturing method thereof |
| CN103367743A (en) * | 2012-03-27 | 2013-10-23 | Tdk株式会社 | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN103762092A (en) * | 2013-01-29 | 2014-04-30 | 湖北圣犬电池科技有限公司 | Electrolyte, electrode plate, supercapacitor monomer, and supercapacitor and preparation method thereof |
| CN103943376A (en) * | 2013-01-22 | 2014-07-23 | 中国科学院大连化学物理研究所 | Electrolyte of mixed type super capacitor |
| CN105489391A (en) * | 2015-12-16 | 2016-04-13 | 山东精工电子科技有限公司 | High-energy and high-power density lithium-ion super capacitor |
| WO2016101331A1 (en) * | 2014-12-25 | 2016-06-30 | 华北理工大学 | Ultra-low temperature chlorine salt aqueous super capacitor electrolyte |
| CN106206063A (en) * | 2016-08-13 | 2016-12-07 | 代相臣 | Water system hybrid super capacitor and preparation method thereof |
| CN113936927A (en) * | 2020-07-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | High-voltage aqueous electrolyte and application thereof |
-
2009
- 2009-03-06 CN CN 200910037614 patent/CN101494123A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000386A (en) * | 2011-09-15 | 2013-03-27 | 海洋王照明科技股份有限公司 | Super hybrid capacitor and manufacturing method thereof |
| CN103367743A (en) * | 2012-03-27 | 2013-10-23 | Tdk株式会社 | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| US9263736B2 (en) | 2012-03-27 | 2016-02-16 | Tdk Corporation | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN103943376A (en) * | 2013-01-22 | 2014-07-23 | 中国科学院大连化学物理研究所 | Electrolyte of mixed type super capacitor |
| CN103762092A (en) * | 2013-01-29 | 2014-04-30 | 湖北圣犬电池科技有限公司 | Electrolyte, electrode plate, supercapacitor monomer, and supercapacitor and preparation method thereof |
| CN103762092B (en) * | 2013-01-29 | 2017-02-22 | 湖北圣融科技有限公司 | Electrolyte, electrode plate, supercapacitor monomer, and supercapacitor and preparation method thereof |
| WO2016101331A1 (en) * | 2014-12-25 | 2016-06-30 | 华北理工大学 | Ultra-low temperature chlorine salt aqueous super capacitor electrolyte |
| CN105489391A (en) * | 2015-12-16 | 2016-04-13 | 山东精工电子科技有限公司 | High-energy and high-power density lithium-ion super capacitor |
| CN106206063A (en) * | 2016-08-13 | 2016-12-07 | 代相臣 | Water system hybrid super capacitor and preparation method thereof |
| CN113936927A (en) * | 2020-07-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | High-voltage aqueous electrolyte and application thereof |
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