CN101719420B - Super capacitance storage battery - Google Patents
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- CN101719420B CN101719420B CN2009102098751A CN200910209875A CN101719420B CN 101719420 B CN101719420 B CN 101719420B CN 2009102098751 A CN2009102098751 A CN 2009102098751A CN 200910209875 A CN200910209875 A CN 200910209875A CN 101719420 B CN101719420 B CN 101719420B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a super capacitance storage battery comprising a positive plate, a negative plate, a clapboard and electrolyte. The super capacitance storage battery is characterized in that the positive plate is a lead storage battery positive plate and at least one of the negative plates is a compound negative plate which is formed by adding a granular capacitance electrode material in a common lead storage battery negative plate diachylum formula. In the invention, the granular capacitance electrode material is added in the negative plate diachylum formula and formed by coating an active carbon material through a conductive material and has excellent conductivity; in addition, the material has improved density after prepared into granules by milling, can form a conductive network which has wide addition proportion range and strengthens active substances of the negative plate, reduce the internal resistance, improve the output power and improve the utilization rate of the active substance of the negative plate while fully playing the capacitance performance without changing the basic structure of the active substance of the negative plate, thereby prolonging the service life of the battery under the condition of high-rate partial charge (HRPSoC).
Description
Technical field
The invention belongs to the electrochemical energy storing device field, be specifically related to a kind of novel super capacitance storage battery.
Background technology
Along with constant development of economy, the energy, resource and environment etc. becomes the focal issue of society, seeks cleaning, the energy renewable and resource-conserving and be the very urgent and difficult task of human society.
The cost performance of all kinds of lead accumulators is high, and fail safe is good, and working service is convenient, mature production technology and and environmental friendliness, renewable, become the first-selected storage battery of all kinds of motor vehicles, communication power supply and ups power etc. just day by day.Yet; Because the limitation of lead accumulator electrochemical system, the mass density of battery and power density are all lower, and the cycle life of battery is lower when using as electrokinetic cell; During particularly as the energy-storage battery of photovoltaic system and wind generator system and Hybrid Vehicle battery; Under high magnification partial charging (HRPSoC) situation, sulfate very easily takes place and gathers and lost efficacy in the negative plate of battery, and the useful life of storage battery is very undesirable.
Ultracapacitor is the novel green energy storage device that grew up in the last few years, has the fast charging and discharging characteristic, power density big (being more than tens times of common batteries), and (cycle-index can reach more than 100,000 times) has extended cycle life.Based on these special performances, ultracapacitor has extraordinary application prospect.Yet,, limited the range of application of ultracapacitor widely although its energy density far above conventional capacitor, significantly is lower than storage battery.
Super capacitance storage battery (also can be described as super accumulator) is a kind of novel energy-storing system that storage battery is combined with ultracapacitor; This system possesses the advantage of storage battery and ultracapacitor simultaneously; Owing to the cushioning effect of ultracapacitor, battery sulfuric acid salt gathers and obtains better inhibited in the high power charging-discharging process, can effectively prolong the cycle life of storage battery in addition; Improve power density, further expand the range of application of storage battery.It (is that storage battery is a main power source that storage battery has outer the connection with the compound mode of ultracapacitor; Ultracapacitor is an accessory power supply, through additional electronic installation both parallel connections is combined into a system) with (being that both directly are combined in the same system) dual mode of interior the connection.Existing research shows, inner connection mode can obtain excellent more performance, and the fast nothing of system response postpones; Do not need simultaneously extra, expensive electronic devices, cost is low, and extraordinary development prospect is arranged.
Patent 200710035835.0 has been announced dual pole plate for super accumulator, and this patent adds gluey nano-sized carbon in electrolyte in the pole plate formation process, and carbon oozes to the negative plate surface when changing into, and finally forms the structure of carbon lead-sheathing, processes the negative plate of charged capacitive.As everyone knows; The capacitive character of material is by index decisions such as its specific area, bulk density and middle porositys; It is inappreciable that the capacitive character of the carbon film that therefore is made up of acetylene black and carbon fiber etc. is compared with the ultracapacitor special-purpose activated charcoal, and the thickness of carbon film is also unsuitable blocked up, otherwise can influence the diffusion of electrolyte; The described method of this patent has certain effect for slim pole plate; Inapplicable for thick type pole plate, versatility is poor.
Patent 200810136633.1 has been announced sealing lead-acid cell for carbon plate negative plate, and this patent has the part negative plate to adopt carbon plate in battery, and carbon plate has certain capacitive character.Patent 200810136634.6 has been announced combined type negative plate sealed lead acid battery, and this patent carbon plate that in battery, laterally arranges on the negative plate is provided with barrier film between negative plate and the carbon plate, and negative plate is connected through lug with carbon plate.Yet these two patents all have limitation, and 1. the capacitance of carbon plate is compared much smallerly with negative plate, and the capacity that carbon plate can reduce battery is set, and reduce the energy density of battery, and influence is very big for small-capacity cells.2. the absolute capacitance amount of carbon plate is little, for high capacity cell, in charge and discharge process the cushioning effect that rises very limited.
There is bibliographical information in the battery terminal negative plate prescription, directly to add absorbent charcoal material, increases the capacitive character of negative plate, process super capacitance cell.Because the conductivity of active carbon is relatively poor, can cause after the interpolation that the negative plate internal resistance increases.In addition because the density and the lead powder of active carbon differ very big; The voidage of negative plate rises significantly behind the interpolation active carbon, and negative plate is very easily oxidized, causes the hyperpolarization of negative plate hypopolarization and positive plate; Shorten storage battery useful life, so the addition of active carbon there is certain limitation.
The capacitance storage battery that existing technology is made; Its capacitive character is very limited; Undesirable for battery in the prolongation effect in partial charging (PSoC) situation following useful life, therefore do not meet the instructions for use of electric motor car power, the following vehicle (hybrid vehicle) of battery and solar energy photovoltaic system.
Summary of the invention
The present invention seeks to: low cell integrated power density and the little shortcoming of cycle life of causing of, positive and negative pole active matter utilance poor for the capacitive character that overcomes capacitance electrode in the existing super capacitance storage battery; And provide a kind of lead accumulator and the asymmetric ultracapacitor combination of lead oxide/carbon are the super capacitance storage battery of one; Not only possess electrochemical double-layer energy storage, high power density, the high current charge-discharge of ultracapacitor and the characteristics that have extended cycle life; And the characteristics that possess storage battery high capacity density, high performance-price ratio simultaneously; And control capacittance property in a wider context; Improve the utilance of positive and negative pole active matter, reduce the influence of the introducing of capacitance electrode material greatly storage battery energy density.
Technical scheme of the present invention is: a kind of super capacitance storage battery; Comprise positive plate, negative plate, dividing plate and electrolyte; It is characterized in that said positive plate is a positive plate of lead storage battery, and in the said negative plate at least one added the graininess capacitance electrode material and the combined type negative plate processed in common lead accumulator negative plate lead paste formula.
The negative plate of combined type described in the present invention is that capacitance electrode material is processed granular substance; And with sneaking into the combined type negative plate lead plaster of processing charged capacitive in the common lead accumulator negative plate lead plaster of becoming reconciled behind deionized water dipping and the suction filtration by a certain percentage; Be coated on then on the negative electrode grid, after curing, drying, process.
Capacitance electrode material described in the present invention specifically is made up of material with carbon element, conductive agent and adhesive, and their percentage by weights separately are: material with carbon element 30～90%, conductive agent 3～50%, adhesive 5～25%; Wherein said material with carbon element is a kind of or mixture more than two kinds in active carbon, CNT, carbon nano-fiber, carbon/charcoal compound, graphitization active carbon and the carbon aerosol; Said conductive agent is a kind of or mixture more than two kinds in carbon black, acetylene black, graphite, the expanded graphite carbon fiber; Said adhesive is one or more the mixture in PTFE, PVDF, fluorubber, CMC and the neoprene.
Among the present invention above-mentioned capacitance electrode material processed the method for granular substance; With reference to prior art; Specific as follows: as at first, to become dough, on roll forming machine, be pressed into film through partial desiccation with capacitance electrode material water or absolute ethyl alcohol or other organic solvent furnishing slurries; Perhaps pass through roll extrusion, drying, process certain thickness film, last bone dry is processed tablet, through pulverizing, suitably milling and process granular substance.Also can add an amount of water/absolute ethyl alcohol or other organic solvents and capacitance electrode material mixed (annotate, solid binder adds after must using suitable dissolution with solvents) with batch mixer, granular substance is processed in directly granulation on roll forming machine.
Volume ratio when the accumulator negative plate of common lead described in the present invention lead plaster mixes with the graininess capacitance electrode material is 1: 0.001～5.
Common lead accumulator negative plate lead plaster is according to conventional proportioning manufacturing among the present invention; Perhaps also can suitably add conductive agent; Said conductive agent is a kind of or mixture more than two kinds in carbon black, acetylene black, graphite, the expanded graphite carbon fiber, and the addition of conductive agent accounts for 0.01%～5% of plumbous weight in the common lead accumulator negative plate lead paste formula.The same with prior art, common lead accumulator negative plate lead plaster can with process three types of sticking type, sand mold and transiens.
Can all be coated with combined type negative plate lead plaster on the negative electrode grid described in the present invention; Perhaps at regional area coating combined type negative plate lead plaster, and other zone coating common lead accumulator negative plate lead plasters, described regional area is meant zone or regional more than two in upper and lower, left and right and middle and the corner of negative electrode grid; Perhaps earlier behind the coating combined type negative plate lead plaster, be coated with common lead accumulator negative plate lead plaster again in the appearance of combined type negative plate lead plaster; Perhaps be coated with common lead accumulator negative plate lead plaster earlier, and be coated with combined type negative plate lead plaster again in the appearance of common lead accumulator negative plate lead plaster; Or common lead accumulator negative plate lead plaster and the alternately coating of combined type negative plate lead plaster multilayer.
The alloy of the anode plate grid of positive plate described in the present invention and the negative electrode grid of negative plate can be pure lead or multicomponent lead alloy, but in the described multicomponent lead alloy except that element lead one or more elements among containing element Ca, Sn, Al, Sb, As, S, Bi, the Si also.
The anode plate grid of positive plate described in the present invention and the negative electrode grid of negative plate can be for common casting grids, also can be lead foil punching or die-cut draw in the net grid, also can be lead fabric plate.
Positive and negative pole plate described in the present invention can be assembled by modes such as lamination, folding and coilings, cell integratedly can process rectangle or cylindrical.
Dividing plate described in the present invention is by a kind of among microcellular rubber, PE, PVC, PP, the AGM or material is compound more than two kinds processes; And described electrolyte is aqueous or the colloidal dilute sulfuric acid.
The lead paste formula of positive plate of lead storage battery described in the present invention is a known technology, and the present invention all with reference to prior art, and does not do any qualification to its component and proportioning.And said positive plate of lead storage battery can be processed flat or two kinds of patterns of tubular type with prior art is equally any, among the present invention this is not limited yet.
Advantage of the present invention is:
1. this super capacitance storage battery provided by the present invention; It has added the graininess capacitance electrode material in the negative plate lead paste formula, this material is because with the coating of absorbent charcoal material through conductive carbon material, conductivity is good; And density improved after process rolled and is prepared into particle; It is big to form the adding proportion scope, strengthens the conductive network of positive and negative pole active matter, when giving full play to capacitive property, reduces the utilance of internal resistance, raising power output, raising positive and negative pole active matter; And do not change the basic structure of positive and negative pole active matter, improved the useful life of battery under high magnification partial charging (HRPSoC) situation.
2. this super capacitance storage battery provided by the present invention; The graininess capacitance electrode material that it adds in the negative plate lead paste formula is owing to have porosity characteristic; Expanded the ion channel of negative plate; Help reducing the concentration polarization of negative plate surface reactive material under the heavy-current discharge condition, thereby improve the power density of battery greatly.
Comprehensively; This super capacitance storage battery provided by the present invention; Not only possess electrochemical double-layer energy storage, high power density, the high current charge-discharge of ultracapacitor and the characteristics that have extended cycle life, and possess the characteristics of storage battery high capacity density, high performance-price ratio simultaneously.And control capacittance property in a wider context, improve the utilance of positive and negative pole active matter, reduce the influence of the introducing of capacitance electrode material greatly to storage battery energy density.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Fig. 1 is the profile of super capacitance storage battery monomer of the present invention;
Fig. 2 is the local amplification view of Fig. 1 monomer;
Fig. 3 is a kind of applying structure (local coating combined type negative plate lead plaster) of negative plate surface lead plaster among the present invention;
Fig. 4 is the another kind of applying structure (appearance coating combined type negative plate lead plaster) of negative plate surface lead plaster among the present invention;
Fig. 5 is the another kind of applying structure (inner coating combined type negative plate lead plaster) of negative plate surface lead plaster among the present invention;
Fig. 6 strengthens cyclic test single cycle program sketch map for battery of the present invention;
Fig. 7 strengthens cyclic test unit test program sketch map for battery of the present invention;
Fig. 8 is the embodiment of the invention and Comparative Examples capacity (C2) test result;
Fig. 9 is that the embodiment of the invention and Comparative Examples are strengthened the cyclic test result.
Wherein: 1, positive plate; 11, anode plate grid; 2, negative plate; 21, negative electrode grid; 22, lug; 3, dividing plate; 4, shell; 101, positive plate of lead storage battery lead plaster; 201, combined type negative plate lead plaster; 202, common lead accumulator negative plate lead plaster.
Embodiment
Embodiment 1: this super capacitance storage battery that present embodiment provides is mainly used in electric bicycle, six monomer series-connected being formed by connecting.As shown in Figure 1; Its each monomer comprises and is encapsulated in six positive plates 1 and seven negative plates 2 that are intervally arranged in the shell 4; Then adopt commercial AGM dividing plate 3 (thickness 0.6mm 10KPa) coating continuously between adjacent positive plate 1 and the negative plate 2, and electrolyte is dilute sulfuric acid (density 1.28g/cm
3).
Further combine monomer part sectioned view shown in Figure 2, said positive plate 1 is a positive plate of lead storage battery, and its concrete formation and manufacture method are following:
Anode plate grid 11 is of a size of: 68mm * 44mm * 2.8mm, adopt antimony content 1.6%, and the Pb-Sb-Cd alloy of cadmium content 1.2% is processed.
Coating positive plate of lead storage battery lead plaster 101 on the said anode plate grid 11, these positive plate of lead storage battery lead plaster 101 proportionings are following: lead powder 100Kg, short fiber 0.07Kg, sulfuric acid (1.40g/cm3) 9.8Kg, deionized water 11-12Kg.It is following with system positive plate of lead storage battery lead plaster 101 processes to press said ratio: earlier lead powder and short fiber were done mixed 5 minutes; The deionized water that adds the ionized water total amount 4/5 that accounts for again wets and 10-15 minute; Under the prerequisite of opening the paste mixing machine cooling system, sulfuric acid is slowly added, add continuously back and 15-20 minute; Add the deionized water of an amount of remainder, the apparent density of positive plate of lead storage battery lead plaster 101 is controlled at 4.0-4.1g/cm3.
The anode plate grid 11 of coated positive plate of lead storage battery lead plaster 101 continues to solidify 24 hours under 60 ℃ of temperature, humidity 85-95% condition; Then 60 ℃, humidity less than 50% condition under, continue to process in dry 24 hours positive plate 1.
Said negative plate 2 is combined type negative plates; This combined type negative plate is that capacitance electrode material is processed granular substance; And with sneaking into the combined type negative plate lead plaster 201 of processing charged capacitive in the common lead accumulator negative plate lead plaster 202 of becoming reconciled behind deionized water dipping and the suction filtration by a certain percentage; Be coated on then on the negative electrode grid 21, after curing, drying, process, its concrete formation and manufacture method are following:
Negative electrode grid 21 is of a size of: 68mm * 44mm * 1.7mm, adopt calcium content 0.09%, and the lead-calcium-tin alloy of tin content 0.3% is processed.
Said capacitance electrode material components by weight is following: active carbon 87%, acetylene black 3%, PTFE (content 60%) emulsion 10%, wherein active carbon adopts specific area 1500m
2/ g, middle porosity greater than 40%, the commercialization active carbon of granularity 5-10 μ m.Earlier active carbon and acetylene black were done mixed 5 minutes, used an amount of water/absolute ethyl alcohol furnishing thin pulp shape then, stirred 1-2 hour; Fully mixing drips the PTFE emulsion, after stirring under stirring; Put into 60 ℃ of baking oven bakings 0.5-3 hour, half-dried, dough that material becomes is taken out; Being pressed into thickness on the roll forming machine is the film about 1mm, puts into 100 ℃ of baking oven bakings and processes tablet in 2-4 hour, through pulverizing, suitably milling and process granular substance; Sieve, get less than 50 orders, greater than 200 purpose parts, subsequent use.
Common lead accumulator negative plate lead plaster 202 proportionings: lead powder 100Kg, barium sulfate 0.8Kg, lignin 0.25Kg, acetylene black 0.2Kg, short fiber 0.05Kg, carbon fiber 0.01Kg, sulfuric acid (1.40g/cm3) 7Kg, deionized water 13-14Kg.Earlier lead powder, barium sulfate, lignin, acetylene black, short fiber, carbon fiber are done and mixed 5 minutes; The deionized water that adds the ionized water total amount 4/5 that accounts for again wets and 10-15 minute; Under the prerequisite of unlatching and cream device cooling system, sulfuric acid is slowly added, add continuously back and 15-20 minute; Add the deionized water of an amount of remainder, the apparent density of common lead accumulator negative plate lead plaster 202 is controlled at 4.3～4.4g/cm3.
With the aforementioned graininess capacitance electrode material of processing; With deionized water vacuum impregnation 30 minutes; Vacuum filtration is removed apparent moisture then; Add in the common lead accumulator negative plate lead plaster 202 of becoming reconciled (common lead accumulator negative plate lead plaster mixes according to 1: 0.33 volume ratio with the graininess capacitance electrode material mutually), stir, process combined type negative plate lead plaster 201.
As shown in Figure 2, the said combined type negative plate lead plaster 201 of all coatings (lug 22 parts of negative plate 2 then need not coating) on the negative electrode grid 21 of present embodiment.The negative electrode grid 21 of coated combined type negative plate lead plaster 201 continues to solidify 24 hours under 60 ℃, humidity 85-95% condition; Then 60 ℃, humidity less than 50% condition under, continue to process in dry 24 hours negative plate 2.
Certainly the coating method of lead plaster also can be at regional area coating combined type negative plate lead plaster 201 on the negative electrode grid 21; And other zone coating common lead accumulator negative plate lead plasters 202, described regional area is meant zone or regional more than two in upper and lower, left and right and middle and the corner of negative electrode grid 21.In a kind of applying structure shown in Figure 3, the upper area of negative electrode grid 21 all has been coated with combined type negative plate lead plaster 201, and lower area then has been coated with common lead accumulator negative plate lead plaster 202.
The lead plaster coating method can also be to be coated with common lead accumulator negative plate lead plaster 202 earlier on the negative electrode grid 21, and is coated with combined type negative plate lead plaster 201 again in the appearance of common lead accumulator negative plate lead plaster 202, and its applying structure is as shown in Figure 4.Perhaps can also be first coating combined type negative plate lead plaster 201 on negative electrode grid 21, be coated with common lead accumulator negative plate lead plaster 202 again in the appearance of combined type negative plate lead plaster 201, its applying structure be as shown in Figure 5.
The quality of the final finished of this super capacitance storage battery that present embodiment provides is 3.93Kg, and rated capacity (C2) is 13.78Ah, and present embodiment further carries out the reinforcing life test to it.
In the prior art, the common evaluation model of battery of electric bicycle is meant: during new battery, measure 15A heavy-current discharge index, acceleration, grade climbing performance that check is actual; Life test is meant and is the battery full charge, SoC (that is, and charged state, as follows) 100%; 5A continuous discharge 1h24min, SoC reduces to 30%, replenishes electricity then, and SoC returns to 100%; As a cycling element, so repeatedly, capacity drops to termination in 70% o'clock of rated capacity; Depict the discharge curve of battery, and therefrom extrapolate energy content of battery density, and battery remaining power.
And described reinforcing life test is meant: making battery SoC (is charged state; As follows) remain in 70%～30% scope; Through 15A, the discharge of 5A alternately impinge, termination or capacity dropped to termination in 70% o'clock of rated capacity when minimum load voltage was lower than 10.20V/, depicted the discharge curve of battery; And therefrom extrapolate energy content of battery density, and battery remaining power.
Usually adopt the reinforcing life test model to replace common evaluation model at present, its reason is following:
1. actual environment for use is: operating current is about 5A during the electric bicycle cruising, and electric current is about 15A when quickening perhaps to go up a slope.Usually, through repeatedly/used back 1 repeatedly in many days, until the protection voltage (generally controlling about SoC30%) that reaches batteries, replenish electricity, it is thus clear that the reinforcing life test model and the practical application situation of battery are more approaching, common evaluation model then difference is bigger.
2. during the actual use of electric bicycle, behind the full charge SoC100%, use very lowly until the probability of the protection voltage that reaches batteries continuously, most applications is the partial charging situation, and promptly SoC is lower than 100%, uses repeatedly.It is thus clear that the reinforcing life test model and the practical application situation of battery are more approaching, common evaluation model then difference is bigger.
3. owing to positive material and negative pole lead sulfate such as gather at reason; Storage battery is in the actual cycle use; The impedance meeting of battery progressively increases, and the 15A heavy-current discharge performance descends fast than the 5A discharge performance, and the batteries discharge prevention is basically in acceleration, climbing process.It is thus clear that the reinforcing life test model and the practical application situation of battery are more approaching, common evaluation model then difference is bigger.
Following mask body combines Fig. 6, shown in Figure 7, and it is following that the super capacitance storage battery that embodiment 1 is provided carries out the reinforcing life process of the test: behind the full charge (SoC100%), and 5A continuous discharge 36min, SoC reduces to 70%; 15A discharge 1min, the 5A 3min that discharges carries out 8 times repeatedly, and SoC reduces to 30%; 1.8A charging 2h14min, SoC returns to 70%, as a circulation; Per 10 circulations are a unit, and 1.8A charges to 14.40V/ only after the 10th loop ends, and the constant voltage 14.40V/ 4h that only charges carries out 5A discharge examination capacity C then
2, detect and finish the additional electricity in back, carry out the test of next unit again, after through the reinforcement cyclic test of 32 unit, finish test.The discharge curve of the super capacitance storage battery that final embodiment 1 is provided is as shown in Figure 8, and can draw its energy density through calculating is 42.03Wh/Kg; And as shown in Figure 9, after the reinforcement cyclic test through 32 unit, the residual capacity of the super capacitance storage battery that embodiment 1 is provided is 8.05Ah.
Comparative Examples 1:
Provide common lead accumulator at present, negative plate all adopts the coating of common lead accumulator negative plate lead plaster, and all the other are with embodiment 1.The quality of this lead accumulator finished product is 4.05Kg, and amount capacity (C2) is 12.42Ah.Equally this common lead accumulator is carried out testing like Fig. 6, reinforcing life shown in Figure 7; Its discharge curve is as shown in Figure 8; Through calculating its energy density is 36.80Wh/Kg and as shown in Figure 9; After the reinforcement cyclic test through 32 unit, the residual capacity of this common lead storage battery is 7.27Ah.
This super capacitance storage battery that embodiment 2 provides, the difference of itself and embodiment 1 is following:
Capacitance electrode material proportioning: active carbon 70%, graphite powder 15%, acetylene black 5%, PVDF10%.Earlier active carbon and acetylene black were done mixed 5 minutes, added the solution of the N-methyl pyrrolidone (NMP) of PVDF, use an amount of N-methyl pyrrolidone furnishing thin pulp shape then; Stirred 1-2 hour; Abundant mixing, roll extrusion on the mirror face stainless steel plate, drying, processing thickness is the film about 1mm; Put into 100 ℃ of baking oven bakings 2-4 hour again, make it bone dry.To process tablet, through pulverizing, suitably milling and process granular substance; Sieve, get less than 50 orders, greater than 200 purpose parts, subsequent use.
With the graininess capacitance electrode material of processing; With deionized water vacuum impregnation 30 minutes; Vacuum filtration is removed apparent moisture then; Add in the common lead accumulator negative plate lead plaster (its proportioning is with embodiment 1) of becoming reconciled (common lead accumulator negative plate lead plaster mixes according to 1: 0.14 volume ratio with the graininess capacitance electrode material mutually), stir, process combined type negative plate lead plaster.
All the other are then with embodiment 1.
The quality of this super capacitance storage battery finished product that present embodiment provides is 3.97Kg; Rated capacity (C2) is 14.73Ah, and through testing like Fig. 6, reinforcing life shown in Figure 7, its discharge curve is as shown in Figure 8; Through calculating its energy density is 44.50Wh/Kg; And as shown in Figure 9, after its reinforcement cyclic test through 32 unit, residual capacity is 7.74Ah.
Comparative Examples 2:
With Comparative Examples 1.
The above is merely preferred embodiment of the present invention, and the various variations that those skilled in the art carries out in not breaking away from claim limited range of the present invention all should be in protection scope of the present invention.
Claims (7)
1. super capacitance storage battery; Comprise positive plate (1), negative plate (2), dividing plate (3) and electrolyte; It is characterized in that said positive plate (1) is a positive plate of lead storage battery; And in the said negative plate (2) at least one added the graininess capacitance electrode material and the combined type negative plate processed in common lead accumulator negative plate lead paste formula; This combined type negative plate is that capacitance electrode material is processed granular substance; And with sneaking into the combined type negative plate lead plaster (201) of processing charged capacitive in the common lead accumulator negative plate lead plaster (202) of becoming reconciled behind deionized water dipping and the suction filtration by a certain percentage, be coated on then on the negative electrode grid (21), after curing, drying, process; Said capacitance electrode material is made up of material with carbon element, conductive agent and adhesive, and their percentage by weights separately are: material with carbon element 30～90%, conductive agent 3～50%, adhesive 5～25%; Wherein said material with carbon element is a kind of or mixture more than two kinds in active carbon, CNT, carbon nano-fiber, carbon/charcoal compound, graphitization active carbon and the carbon aerosol; Said conductive agent is a kind of or mixture more than two kinds in carbon black, acetylene black, graphite, the expanded graphite carbon fiber; Said adhesive is one or more the mixture in PTFE, PVDF, fluorubber, CMC and the neoprene; And the volume ratio when said common lead accumulator negative plate lead plaster (202) mixes with the graininess capacitance electrode material is 1: 0.001～5.
2. according to the described super capacitance storage battery of claim 1; It is characterized in that common lead accumulator negative plate lead plaster (202) is according to conventional proportioning manufacturing; Perhaps suitably add conductive agent; Said conductive agent is a kind of or mixture more than two kinds in carbon black, acetylene black, graphite, the expanded graphite carbon fiber, and the addition of conductive agent accounts for 0.01%～5% of plumbous weight in common lead accumulator negative plate lead plaster (202) prescription.
3. according to the described super capacitance storage battery of claim 1, it is characterized in that said negative electrode grid (21) upward all is coated with combined type negative plate lead plasters (201); Perhaps at regional area coating combined type negative plate lead plaster (201); And other zone coating common lead accumulator negative plate lead plasters (202), described regional area is meant zone or regional more than two in upper and lower, left and right and middle and the corner of negative electrode grid (21); Perhaps earlier behind the coating combined type negative plate lead plaster (201), be coated with common lead accumulator negative plate lead plaster (202) again in the appearance of combined type negative plate lead plaster (201); Perhaps be coated with common lead accumulator negative plate lead plaster (202) earlier, and be coated with combined type negative plate lead plaster (201) again in the appearance of common lead accumulator negative plate lead plaster (202); Or common lead accumulator negative plate lead plaster (202) and the alternately coating of combined type negative plate lead plaster (201) multilayer.
4. according to the described super capacitance storage battery of claim 1; The material of negative electrode grid (21) that it is characterized in that anode plate grid (11) and the negative plate (2) of said positive plate (1) is multicomponent lead alloy, except that element lead, goes back a kind of among containing element Ca, Sn, Al, Sb, As, S, Bi, the Si in the described multicomponent lead alloy or element more than two kinds.
5. according to the described super capacitance storage battery of claim 1, the negative electrode grid (21) that it is characterized in that anode plate grid (11) and the negative plate (2) of said positive plate (1) is common casting grid, lead foil punching or die-cut and draws in the net a kind of in grid, the lead fabric plate.
6. according to the described super capacitance storage battery of claim 1, it is characterized in that said positive plate (1) and negative plate (2) press a kind of assembling in lamination, the folding and winding method, the cell integrated rectangle or cylindrical of processing.
7. according to the described super capacitance storage battery of claim 1, it is characterized in that said dividing plate (3) is by a kind of among microcellular rubber, PE, PVC, PP, the AGM or material is compound more than two kinds to process; And described electrolyte is aqueous or the colloidal dilute sulfuric acid.
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| CN102709567A (en) * | 2012-06-18 | 2012-10-03 | 奇瑞汽车股份有限公司 | Lead-acid cell |
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| CN102024568B (en) * | 2010-06-30 | 2012-06-06 | 南京双登科技发展研究院有限公司 | Manufacture method of high-capacity inorganic super capacitor electrode plates |
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| CN102903895B (en) * | 2011-03-18 | 2014-11-12 | 哈尔滨工业大学 | Electrode material for super lead acid battery, preparation method of electrode material and method for preparing cathode of super lead acid battery by using electrode material |
| CN102157735B (en) * | 2011-03-18 | 2013-02-27 | 哈尔滨工业大学 | Electrode material used for super lead-acid battery, preparation method thereof, and method for preparing cathode of super lead-acid battery by utilizing same |
| EP2715840B1 (en) * | 2011-06-03 | 2015-05-27 | Basf Se | Carbon-lead blends for use in hybrid energy storage devices |
| CN102340047B (en) * | 2011-09-30 | 2014-12-24 | 钟阳 | High-power winding-type lead-carbon super storage battery |
| CN102856591B (en) * | 2012-10-08 | 2016-01-20 | 中国电子科技集团公司第十八研究所 | The preparation method of high-capacity lithium-manganese battery |
| CN105322209A (en) * | 2014-07-11 | 2016-02-10 | 陈锦棠 | Quickly charged battery |
| CN104851595A (en) * | 2015-06-04 | 2015-08-19 | 遂宁宏成电源科技有限公司 | Super capacitor battery |
| JP6775764B2 (en) | 2016-09-30 | 2020-10-28 | 株式会社Ｇｓユアサ | Lead-acid battery |
| CN109755516B (en) * | 2018-12-29 | 2021-10-08 | 苏州大学 | Adhesive lead-carbon composite cathode |
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| CN102709567A (en) * | 2012-06-18 | 2012-10-03 | 奇瑞汽车股份有限公司 | Lead-acid cell |
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| CN101719420A (en) | 2010-06-02 |
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