CN103000390B - A kind of negative pole currect collecting preparation and use the ultracapacitor of this collector - Google Patents
A kind of negative pole currect collecting preparation and use the ultracapacitor of this collector Download PDFInfo
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- CN103000390B CN103000390B CN201210569017.XA CN201210569017A CN103000390B CN 103000390 B CN103000390 B CN 103000390B CN 201210569017 A CN201210569017 A CN 201210569017A CN 103000390 B CN103000390 B CN 103000390B
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- 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
Abstract
The present invention proposes a kind of negative pole currect collecting preparation, it is characterized in that comprising the steps: 1) negative current collector is put into high-temperature acidic solution and flood a period of time; 2) wash away surface acidity solution, dry; 3) coated metal oxide layer, dries; 4) apply carbonaceous material layer, dry.The present invention also proposes a kind of ultracapacitor using the negative current collector of above-mentioned preparation method, be made up of positive plate, negative plate, barrier film and acidic electrolysis bath, it is characterized in that the active material of described positive plate is made up of the oxide of lead, the active material of described negative plate adopts porous carbon material.Ultracapacitor of the present invention, has high-energy-density (18 ~ 25Wh/Kg), long circulation life (& gt; 15000 times), can be applied in well in the occasion of ask for something high-energy, long life.
Description
Technical field
The present invention relates to supercapacitor technologies field, particularly a kind of negative pole currect collecting preparation and use the ultracapacitor of this collector.
Background technology
Ultracapacitor develops a kind of chemical energy storage device rapidly in recent ten years, overall performance is between traditional capacitor and battery, its outstanding advantage is that the charging interval is short, discharge power is large, charge and discharge circulation life is long, so, be widely used in the fields such as consumer electronics back-up source, hybrid vehicle, wind power generation, high power UPS at present.But ultracapacitor compares battery, energy is on the low side, thus limits its use in ask for something high-energy-density occasion.
At present, in order to improve the energy density of ultracapacitor, the asymmetric structural design of general employing, namely a pole of ultracapacitor adopts the electrode (as nickel hydroxide, brown lead oxide, LiMn2O4, lithium titanate etc.) of battery, another pole adopts the electrode (as active carbon, mesoporous carbon, charcoal-aero gel etc.) of double electric layer capacitor, and has successively occurred nickel hydroxide (Ni (OH)
2)/potassium hydroxide (KOH)/active carbon (C), brown lead oxide (PbO
2)/sulfuric acid (H
2sO
4)/active carbon (C), LiMn2O4 (LiMn
2o
4)/lithium sulfate (Li
2sO
4)/active carbon (C), nickle cobalt lithium manganate (LiNi
1/3co
1/3mn
1/3o
2)/hexafluoro phosphorus lithium (LiPF
6the systems such as)+ethylene carbonate (EC)+methyl ethyl carbonate (EMC)/active carbon (C), the asymmetrical type super capacitor energy density of these types can reach 10-25Wh/Kg, wherein PbO
2/ H
2sO
4/ C asymmetrical type ultracapacitor is because cost is low, energy density higher (can reach 15-25Wh/Kg), and combination property is better, becomes a class asymmetrical type capacitor of most Commercial Prospect.From PbO
2/ H
2sO
4the relevant report of/C asymmetrical type ultracapacitor performance, at present, the main deficiency of this kind of ultracapacitor is that charge and discharge circulation life is too low, general at 1000 ~ 2000 times, the highest also can only reach 5000 times, compared with the ultracapacitor of other long circulation life, have a long way to go, also limit its applying commercially.
At PbO
2/ H
2sO
4in/C asymmetrical type ultracapacitor, charge and discharge circulation life is on the low side key factor is in charcoal negative pole poor stability, and this Carbon Materials associativity mainly due to one side negative current collector and high-specific surface area is poor; There is corrosion in negative current collector on the other hand in charge and discharge process, and these have had a strong impact on the stability of ultracapacitor work.
Summary of the invention
In order to address these problems well, the present invention proposes and a kind ofly form the method for multilayer transition layer and anti-corrosion layer in negative terminal surface by chemical treatment and physical treatment, effectively improving the cycle life of ultracapacitor, meet the requirement that the long-life uses.
The present invention proposes a kind of negative pole currect collecting preparation, it is characterized in that comprising the steps:
1) negative current collector is put into high-temperature acidic solution and flood a period of time;
2) wash away surface acidity solution, dry;
3) coated metal oxide layer, dries;
4) apply carbonaceous material layer, dry.
Wherein, described high-temperature acidic solution to be temperature be 35 ~ 45 DEG C sulfuric acid, hydrochloric acid, phosphoric acid or aqueous acetic acid; The mass percent concentration of high-temperature acidic solution is 10 ~ 30%.
Wherein, described dip time is 5 ~ 30 minutes.
Wherein, described metal oxide layer is made up of one or more in titanium oxide, sub-titanium oxide, barium monoxide, strontium oxide strontia, bismuth oxide, tin oxide, molybdenum oxide, barium monoxide, tungsten oxide.
Wherein, described carbonaceous material layer is made up of one or more in conductive black, acetylene black, native graphite, electrographite, MCMB, intermediate-phase carbon fiber, vapor-grown carbon fibers, hard charcoal, soft charcoal, petroleum coke, Graphene, fullerene, carbon nanotube, glass-like carbon.
More preferably, also add polymeric binder in described metal oxide layer and carbonaceous material layer, described polymeric binder is made up of one or more receiving in (HPMC), polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR) of CMC (CMC), hydroxypropyl methylcellulose.
Wherein, in described metal oxide layer, each material proportion is metal oxide: polymeric binder=(75 ~ 95): (5 ~ 25); In described carbonaceous material layer, each material proportion is carbonaceous material: polymeric binder=(80 ~ 90): (10 ~ 20).
Wherein, the thickness of described metal oxide layer is more than 10 μm; The thickness of described carbonaceous material layer is more than 20 μm.
Wherein, described negative current collector is slab construction, network structure or lattice structure, and material is pure lead or lead alloy.
The present invention also proposes a kind of ultracapacitor using the negative current collector of above-mentioned preparation method, be made up of positive plate, negative plate, barrier film and acidic electrolysis bath, it is characterized in that the active material of described positive plate is made up of the oxide of lead, the active material of described negative plate adopts porous carbon material.
Wherein, described porous carbon material comprises active carbon, mesoporous carbon, charcoal-aero gel, Carbon foam, charcoal felt or charcoal cloth.
Wherein, described lead alloy is the one in lead-antimony alloy, plumbous antimony arsenic alloy, lead-calcium alloy, terne metal, lead-calcium-tin alloy, Pb-Ca-Sn-Al alloy.
Wherein, described barrier film comprises fibreglass diaphragm, phenolic resins barrier film, mipor scheider, polyvinyl chloride (PVC) barrier film, polyethylene (PE) barrier film, polypropylene (PP) barrier film.
Wherein, described acidic electrolysis bath is 1.10 ~ 1.35g/cm
3aqueous sulfuric acid.
The ultracapacitor using the technology of the present invention to make, has high-energy-density (18 ~ 25Wh/Kg), long circulation life (>15000 time), can be applied in well in the occasion of ask for something high-energy, long life.
Embodiment
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment.
The present invention proposes a kind of high-energy ultracapacitor, by positive plate, negative plate, barrier film and acidic electrolysis bath composition, wherein positive plate adopts lead dioxide electrode, the active material of negative plate adopts porous carbon material, negative current collector adopts pure lead, lead-antimony alloy, plumbous antimony arsenic alloy, lead-calcium alloy, terne metal, lead-calcium-tin alloy, Pb-Ca-Sn-Al alloy, first collector is put into high-temperature acidic solution and is processed a period of time, one deck corrosion layer is formed in its surface reaction, after washing away acidic electrolysis bath oven dry, at its surface-coated layer of metal oxide skin(coating), after oven dry, again at its surface-coated one deck carbonaceous material layer, as negative current collector after oven dry.Then active material applied or press on a current collector attached, being made into negative plate.
The active material that in the present invention, negative pole uses is porous carbon material, and these materials generally have the long-pending (1200 ~ 2000m of higher ratio table
2/ g), carrying out energy storage by forming electric double layer, mainly comprising active carbon, mesoporous carbon, charcoal-aero gel, Carbon foam, charcoal felt, charcoal cloth.
In the present invention high-temperature acidic solution be 35 ~ 45 DEG C, mass percent concentration be 10 ~ 30% sulfuric acid, hydrochloric acid, phosphoric acid, aqueous acetic acid.
Metal oxide described in the present invention mainly comprises titanium oxide, sub-titanium oxide, barium monoxide, strontium oxide strontia, bismuth oxide, tin oxide, molybdenum oxide, barium monoxide, tungsten oxide.
Carbonaceous material described in the present invention is the good Carbon Materials of some conductivity, mainly comprises conductive black, acetylene black, native graphite, electrographite, MCMB, intermediate-phase carbon fiber, vapor-grown carbon fibers, hard charcoal, soft charcoal, petroleum coke, Graphene, fullerene, carbon nanotube, glass-like carbon.
Also polymeric binder is added in metal oxide layer described in the present invention and carbonaceous material layer, it is the macromolecular material of some high stabilities in sour environment, mainly comprises CMC (CMC), hydroxypropyl methylcellulose receives (HPMC), polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR).
Barrier film described in the present invention comprises fibreglass diaphragm, phenolic resins barrier film, mipor scheider, polyvinyl chloride (PVC) barrier film, polyethylene (PE) barrier film, polypropylene (PP) barrier film, and its thickness is 0.3 ~ 1.0mm; Described acidic electrolysis bath is 1.10 ~ 1.35g/cm
3aqueous sulfuric acid.
In the present invention, the making step of positive plate is: take a certain amount of lead powder, lead monoxide powder, and add appropriate water and sulfuric acid, then being stirred to paste is coated on grid or foil, green plate is prepared into after drying, solidification, then green plate and lead foil are formed one and change into half pond, activate green plate according to certain discharge and recharge system, the pole plate after activation is brown lead oxide positive plate.
In the present invention, the making step of negative plate is:
(1) negative current collector chemical surface treatment: first collector is put into after high-temperature acidic solution processes a period of time, then wash away the acid solution of remained on surface with deionized water, put into baking oven drying.
(2) coating of negative current collector metal oxide layer: first take a certain amount of metal oxide, polymeric binder, is then stirred to paste and is coated in negative pole currect collecting surface, put into baking oven after drying.
(3) coating of negative current collector carbonaceous material layer: first take a certain amount of carbonaceous material, polymeric binder, is then stirred to paste and is coated in negative pole currect collecting surface, put into baking oven after drying.
(4) negative electrode active material coating or press attached: take a certain amount of porous carbon material, binding agent mixing after, be coated on the collector handled well as stated above after being stirred to paste or roll be pressed into film after press and be attached on processed good collector, be prepared into negative plate after drying.
embodiment 1:
The making of positive plate: by lead powder, lead monoxide powder in mass ratio 45:55 ratio mixing, add appropriate sulfuric acid and water furnishing paste, then be coated on the lead-calcium grid of 1.25mm, after 110 DEG C of-8min dryings, put into after temperature is 45 DEG C, relative humidity is 80% environment solidifies 12h, take out and be made into 120*75*1.25mm
3positive pole green plate.By the positive pole green plate made and lead foil, therebetween is assembled into fibreglass diaphragm and changes into half-cell, injects excessive 1.08g/cm
3aqueous sulfuric acid, fluid injection is after 4 hours, with charge-discharge machine with 4mA/cm
2electric current (being as the criterion with positive plate areal calculation) carry out charging 24 hours, then with 8mA/cm to changing into half-cell
2electric current is discharged to voltage 1.75V to it, is then taken out by the pole plate changed into, clean with deionized water rinsing, at the baking oven inner dryings of 80 DEG C after 1 hour, takes out and uses in order to capacitor assembling.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 22Wh/Kg, through 15000 times circulation after, capability retention is 82.5%.
embodiment 2:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 35 DEG C, mass percent concentration be 25% the quiet stain of aqueous acetic acid 25 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 21.5Wh/Kg, through 15000 times circulation after, capability retention is 84.5%.
embodiment 3:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 35 DEG C, mass percent concentration be 15% the quiet stain of aqueous hydrochloric acid solution 8 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 21.2Wh/Kg, through 15000 times circulation after, capability retention is 81.5%.
embodiment 4:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by sub-titanium oxide (Ti
4o
7), CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 22.5Wh/Kg, through 15000 times circulation after, capability retention is 90.5%.
embodiment 5:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SrO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 21.8Wh/Kg, through 15000 times circulation after, capability retention is 81.2%.
embodiment 6:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by WO
2.39, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by conductive black (CB), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 22.3Wh/Kg, through 15000 times circulation after, capability retention is 85.1%.
embodiment 7:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by crystalline flake graphite, CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 23.2Wh/Kg, through 15000 times circulation after, capability retention is 82.7%.
embodiment 8:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by vapor-grown carbon fibers (VGCF), CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 23.5Wh/Kg, through 15000 times circulation after, capability retention is 83.1%.
embodiment 9:
The making of positive plate: with embodiment 1.
The making of negative plate:
(1) negative current collector chemical surface treatment: be 120*75*1.00mm by overall dimension
3, rush that round-meshed terne metal paper tinsel puts into that temperature is 40 DEG C, mass percent concentration be 20% the quiet stain of aqueous sulfuric acid 10 minutes, taking-up deionized water washes away residual solution, puts into the baking oven inner drying 30 minutes of 80 DEG C, takes out for subsequent use.
(2) coating of negative current collector surface metal oxide layer: by SnO
2, CMC in mass ratio 90:10 take, add appropriate water furnishing paste, be then coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the metal oxide layer thickness of terne metal paper tinsel upper surface is 20 μm.
(3) coating of negative pole currect collecting surface carbonaceous material layer: by Graphene, CMC in mass ratio 85:15 take, add appropriate water furnishing paste, then be coated on the terne metal paper tinsel of above-mentioned process, then put into the baking oven inner drying 1 hour of 100 DEG C, the carbonaceous material layer thickness of terne metal paper tinsel upper surface is 30 μm.
(4) pressure of negative electrode active material is attached: by active carbon, polytetrafluoroethylene in mass ratio 90:10 ratio mixing, then roll the carbon membrane being pressed into 1.0mm, two panels carbon membrane pressure be attached on above-mentioned collector, be made into 120*75*2.5mm
3negative plate.
Select fibreglass diaphragm, 15 positive plates made above-mentioned, 15 negative plates are laminated into battery core, and load in polypropylene plastics shell, injecting 750g density is 1.25g/cm
3aqueous sulfuric acid, after changing into, capacitor is tested, when operating voltage interval be 0.9 ~ 2.1V, measuring current be 30A, the energy density of capacitor is 23.8Wh/Kg, through 15000 times circulation after, capability retention is 83.7%.
According to embodiment test case above, can be summarized as follows:
| Chemical treatment | Metal oxide layer | Carbonaceous material layer | Energy density (Wh/Kg) | 15000 capability retentions (%) |
| 20％ H 2SO 4-40℃-10min | SnO 2:CMC=90:10 | Conductive black: CMC=85:15 | 22 | 82.5 |
| 25％ HAC-35℃-25min | SnO 2:CMC=90:10 | Conductive black: CMC=85:15 | 21.5 | 84.5 |
| 15％ HCL-35℃-8min | SnO 2:CMC=90:10 | Conductive black: CMC=85:15 | 21.2 | 81.5 |
| 20％ H 2SO 4-40℃-10min | Ti 4O 7:CMC=90:10 | Conductive black: CMC=85:15 | 22.5 | 90.5 |
| 20％ H 2SO 4-40℃-10min | SrO 2:CMC=90:10 | Conductive black: CMC=85:15 | 21.8 | 81.2 |
| 20％ H 2SO 4-40℃-10min | WO 2.39:CMC=90:10 | Conductive black: CMC=85:15 | 22.3 | 85.1 |
| 20％ H 2SO 4-40℃-10min | SnO 2:CMC=90:10 | Crystalline flake graphite: CMC=85:15 | 23.2 | 82.7 |
| 20％ H 2SO 4-40℃-10min | SnO 2:CMC=90:10 | VGCF：CMC＝85：15 | 23.5 | 83.1 |
| 20％ H 2SO 4-40℃-10min | SnO 2:CMC=90:10 | Graphene: CMC=85:15 | 23.8 | 83.7 |
As can be seen from the above table, by the processing method of conversion chemical treatment, metal oxide layer and carbonaceous material layer, the requirement of all kinds of high-energy, long-life application scenario can be met.
Just preferred embodiment of the present invention described in this specification, above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art, all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (12)
1. a negative pole currect collecting preparation, is characterized in that comprising the steps:
1) negative current collector is put into high-temperature acidic solution and flood a period of time;
2) wash away surface acidity solution, dry;
3) coated metal oxide layer, dries;
4) apply carbonaceous material layer, dry;
Wherein, described high-temperature acidic solution to be temperature be 35 ~ 45 DEG C sulfuric acid, hydrochloric acid, phosphoric acid or aqueous acetic acid; The mass percent concentration of high-temperature acidic solution is 10 ~ 30%; Described dip time is 5 ~ 30 minutes.
2. preparation method as claimed in claim 1, is characterized in that described metal oxide layer is made up of one or more in titanium oxide, sub-titanium oxide, barium monoxide, strontium oxide strontia, bismuth oxide, tin oxide, molybdenum oxide, barium monoxide, tungsten oxide.
3. preparation method as claimed in claim 1, is characterized in that described carbonaceous material layer is made up of one or more in conductive black, acetylene black, native graphite, electrographite, MCMB, intermediate-phase carbon fiber, vapor-grown carbon fibers, hard charcoal, soft charcoal, petroleum coke, Graphene, fullerene, carbon nanotube, glass-like carbon.
4. preparation method as claimed in claim 2 or claim 3, it is characterized in that also adding polymeric binder in described metal oxide layer and carbonaceous material layer, described polymeric binder is made up of one or more in sodium carboxymethylcellulose (CMC), hydroxypropyl methylcellulose sodium (HPMC), polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA), butadiene-styrene rubber (SBR).
5. preparation method as claimed in claim 4, is characterized in that in described metal oxide layer, each material proportion is metal oxide: polymeric binder=(75 ~ 95): (5 ~ 25); In described carbonaceous material layer, each material proportion is carbonaceous material: polymeric binder=(80 ~ 90): (10 ~ 20).
6. preparation method as claimed in claim 1, is characterized in that the thickness of described metal oxide layer is more than 10 μm; The thickness of described carbonaceous material layer is more than 20 μm.
7. preparation method as claimed in claim 1, it is characterized in that described negative current collector is slab construction, network structure or lattice structure, material is pure lead or lead alloy.
8. preparation method as claimed in claim 7, is characterized in that described lead alloy is the one in lead-antimony alloy, plumbous antimony arsenic alloy, lead-calcium alloy, terne metal, lead-calcium-tin alloy, Pb-Ca-Sn-Al alloy.
9. use the preparation method as described in one of claim 1-8 to prepare the ultracapacitor of negative current collector, be made up of positive plate, negative plate, barrier film and acidic electrolysis bath, it is characterized in that the active material of described positive plate is made up of the oxide of lead, the active material of described negative plate adopts porous carbon material.
10. ultracapacitor as claimed in claim 9, is characterized in that described porous carbon material comprises active carbon, mesoporous carbon, charcoal-aero gel, Carbon foam, charcoal felt or charcoal cloth.
11. ultracapacitors as claimed in claim 9, is characterized in that described barrier film comprises fibreglass diaphragm, phenolic resins barrier film, mipor scheider, polyvinyl chloride (PVC) barrier film, polyethylene (PE) barrier film, polypropylene (PP) barrier film.
12. ultracapacitors as claimed in claim 9, is characterized in that described acidic electrolysis bath is 1.10 ~ 1.35g/cm
3aqueous sulfuric acid.
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| CN105448533B (en) * | 2014-12-19 | 2018-04-10 | 中国科学院福建物质结构研究所 | A kind of combination electrode and preparation method thereof and the application in ultracapacitor |
| CN104851603A (en) * | 2015-04-02 | 2015-08-19 | 安徽江威精密制造有限公司 | Modified waste PVC-based active carbon-loaded nano arsenic sulfide composite electrode material and preparation method thereof |
| CN104851595A (en) * | 2015-06-04 | 2015-08-19 | 遂宁宏成电源科技有限公司 | Super capacitor battery |
| WO2017000219A1 (en) * | 2015-06-30 | 2017-01-05 | 张雨虹 | Doped conductive oxide and improved electrochemical energy storage device polar plate based on same |
| CN105869913B (en) * | 2016-04-06 | 2018-07-20 | 江苏中天科技股份有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN108063283B (en) * | 2017-12-05 | 2020-06-05 | 陆文飞 | Lead-calcium internalization colloid electrolyte and preparation method thereof |
| CN111816846A (en) * | 2020-07-03 | 2020-10-23 | 肇庆理士电源技术有限公司 | Graphene doping-based lead-carbon battery negative grid and preparation method thereof |
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