CN100555715C - A kind of lead-acid accumulator anode diachylon - Google Patents
A kind of lead-acid accumulator anode diachylon Download PDFInfo
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- CN100555715C CN100555715C CNB2007101518925A CN200710151892A CN100555715C CN 100555715 C CN100555715 C CN 100555715C CN B2007101518925 A CNB2007101518925 A CN B2007101518925A CN 200710151892 A CN200710151892 A CN 200710151892A CN 100555715 C CN100555715 C CN 100555715C
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lead-acid accumulator anode diachylon, comprise lead powder, 1.4g/cm
3Sulfuric acid, deionized water, brown lead oxide, short fiber, carbon fiber, anisotropy graphite and bismuth oxide, wherein each composition accounts for the percentage by weight of lead powder and is: lead powder 100%, 1.4g/cm
3Sulfuric acid 8～12%, deionized water 9～11%, brown lead oxide 3～4.2%, short fiber 0.05～0.06%, carbon fiber 0.10～0.15%, anisotropy graphite 0.2～0.4%, bismuth oxide 0.05～0.11%.On the basis of the present invention certain water and acid content in active material, add multiple anode active substances such as anisotropy graphite, bismuth oxide, the proportioning of various compositions changes again, can not only increase the initial capacity and the gravimetric specific energy of battery, and the cycle life that can prolong battery.
Description
Technical field
The present invention relates to a kind of lead acid battery positive electrode.
Background technology
Because the UPS stand-by power supply had very large market at nearly more than 20 years, and many advantage such as the voltage that valve-regulated lead-acid battery itself is had is higher relatively, and price is lower, and use is non-maintaining, firmly in occupation of the biggest market share in this field.And the valve-regulated lead-acid battery of China, although firmly occupied the great market share of world's lead acid accumulator already, but progressive little aspect the life-span with respect to flooded batteries, tracing it to its cause mainly is that the positive pole of these batteries is not carried out, and the inefficacy in advance of positive active material has caused battery life to descend fast.And anodal influence to battery life is mainly derived from the anode diachylon prescription.At present, the lead plaster of practical application has sticking type lead plaster, sand mold lead plaster and other types such as water cream etc., and lead paste formula influences the phase composition of green plate and ripe pole plate to a great extent, and then influences capacity, life-span and other performances of battery.In prescription, concerning a certain amount of lead powder amount, the increase water yield and sour amount can improve the active material porosity in the lead plaster, reduce its superficial density, but can reduce the intensity of active material.Most manufacturer the pole plate lead paste formula and and cream technique aspect similar, so the quality level of battery also is more or less the same.The measure of adopting mainly is conductive agent, an adhesive in filling a prescription by increase, (triplicity together for fiber, be used) content increase the initial performance of battery, and improve active material utilization by improving porosity, to increase the gravimetric specific energy of battery, and the adding of excess binder, fiber has had a strong impact on the charge acceptance of battery, increase the internal resistance of cell, shortened dramatically the useful life of battery.That is to say the active material composition that passes through in prescription, directly to add conductive agent, adhesive, fiber aspect at present, be difficult to make the initial capacity of battery and cycle life to take into account simultaneously.
Summary of the invention
The objective of the invention is at the problems referred to above, a kind of lead-acid accumulator anode diachylon is provided, not only can increase the initial capacity and the gravimetric specific energy of battery, and the cycle life that can prolong battery.
Technical scheme of the present invention is: a kind of lead-acid accumulator anode diachylon comprises lead powder, 1.4g/cm
3Sulfuric acid, deionized water, brown lead oxide, short fiber, carbon fiber, anisotropy graphite and bismuth oxide, wherein each composition accounts for the percentage by weight of lead powder and is: lead powder 100%, 1.4g/cm
3Sulfuric acid 8～12%, deionized water 9～11%, brown lead oxide 3～4.2%, short fiber 0.05～0.06%, carbon fiber 0.10～0.15%, anisotropy graphite 0.2～0.4%, bismuth oxide 0.05～0.11%.
Preferably, described deionized water resistivity is more than or equal to 0.6M Ω.
Preferably, described carbon fiber diameter is 0.1～0.9 μ m, and length is 4-6mm, and addition is 0.1% of a lead powder amount.
Preferably, described staple length is 1～2mm, and fineness is 2Denier.9000 meters of length, quality 1 gram are 1 Denier.
Preferably, described anisotropy graphite fineness be 120 orders, residue on sieve less than 1, ash is less than 5, pH value is 6～7.
Beneficial effect of the present invention is: on the basis of the present invention certain water and acid content in active material, add multiple anode active substances such as anisotropy graphite, bismuth oxide, the proportioning of various compositions changes again, can not only increase the initial capacity and the gravimetric specific energy of battery, and the cycle life that can prolong battery.In positive pole, add anisotropy graphite, graphite is oxidized to compound between graphite layers in sulfuric acid medium, cause the irregular expansion of graphite to increase, increased anodal porosity, improve battery and recycled the life-span: in lead plaster, added carbon fiber, carbon fiber is stable in pole plate, conducts electricity very well, and it is than the ratio resistance similar (7 * 10 of resistance to active material
-6Ω m), in active material, forms conductive network, thereby improve the utilance and the charge acceptance of active material, reduce the internal resistance of battery simultaneously, reach the characteristic of guaranteed capacity and life-saving.Brown lead oxide is the positive active material crystal seed, can improve battery forming current efficient, shortens to change into the time, adds red lead relatively in the regular convention formula and will reduce cost; The adding bismuth oxide can be eliminated battery is not had the antimony effect, avoids causing the increase of resistance because of loose contact between grid and the active material.When the present invention makes battery obtain than height ratio capacity, specific energy, increase the intensity of plate active material by additive, thereby prolonged the useful life of battery.
Description of drawings
Fig. 1 is A1 and A4 battery life test curve figure in the embodiment of the invention 1;
Fig. 2 is B1, B2 and B3 battery life test curve figure in the embodiment of the invention 2.
Embodiment
With conventional 6V4AH battery is the sample battery, adopts two kinds of battery structures to carry out orthogonal test.Battery completes that test 20h in back leads and the initial capacity of 3C, gravimetric specific energy and make cycle life according to pet-valve control sealed lead acid battery technical conditions national standard (GBT 19639.1-2005).
Battery adopts Z1.6A 2 positive 3 negative structure assemblings, and Comparative Examples lead paste formula A1～A3 is the modal three kinds of anode diachylon prescriptions of existing practicality.Percentage all is weight percentage described in A1～A4 prescription.
Prescription A1: lead powder 100%, deionized water content are 11% of lead powder, 1.40g/cm
3Sulfuric acid content is 10.5% of a lead powder, and short fibre content is 0.05% of a lead powder.
Prescription A2: lead powder 100%, deionized water content are 11.5% of lead powder, 1.40g/cm
3Sulfuric acid content is 85% of a lead powder, short fibre content be lead powder 0.2%, acetylene black content is 0.5% of lead powder.
Prescription A3: lead powder 100%, deionized water content are 8% of lead powder, 1.40g/cm
3Sulfuric acid content is 11% of a lead powder, and short fibre content is that 0.1% content of graphite of lead powder is 0.8% of a lead powder, and ptfe emulsion content is the 0.08%g of lead powder, adjusts with deionized water content less than 0.8% of lead powder.
Present embodiment prescription A4: lead powder 100%, brown lead oxide content are 3.2% of lead powder, and short fibre content is 0.06% of a lead powder, and carbon fiber content is 0.05% of a lead powder, and deionized water content is 10% of lead powder, 1.40g/cm
3Sulfuric acid content is 10% of a lead powder, and the anisotropy content of graphite is 0.4% of a lead powder, and bismuth oxide content is 0.07% of lead powder.Lead powder, brown lead oxide, anisotropy graphite, short fiber, carbon fiber, bismuth oxide are mixed adding to be closed in the cream machine, stirred 5 minutes, add pure water then apace and stir, add sulfuric acid more lentamente and stir, be mixed with lead plaster and be used for making the 6V4AH battery.
Test all kinds of battery 20h and 3C capacity, compare examination as the battery initial capacity.The discharge data of above-mentioned battery averaged makes following table 1:
All kinds of battery initial performance of table 1 test data/h (min)
| The battery classification | A1 | A2 | A3 | A4 |
| 20h leads | 20h01′ | 20h | 20h42′ | 22h28′ |
| 3C | 8′47″ | 8′11″ | 8′49″ | 9′51″ |
By data in the last table 2 as can be seen: all kinds of batteries, the discharge test 20h that (GB/T19639.1-2005) require that can both be up to state standards leads discharge 20h and 7 minutes requirement of 3C discharge.Adding along with short fiber, carbon raw and other active material in the prescription no matter be that 20h leads capacity or 3C capacity, all shows a rising trend, add anisotropy graphite, carbon fiber simultaneously after, this increase trend is more obvious.
After the battery process initial capacity test passes, test the life-span of going up 4 class batteries in the table 1, the life test data of above-mentioned battery are averaged make following table 2 according to the conventional batteries life test method.Discharge cycles number of times and discharge pond time are made life-span correlation curve Fig. 1 in the record experimentation.
All kinds of battery GB of table 2 cycle life data/time
| Battery types | A1 | A2 | A3 | A4 |
| Cycle-index | 410 | 417 | 425 | 650 |
Can learn from table 2: all 350 times the requirements the overgauge of the GB cycle life of above-mentioned all kinds of batteries, A4 class battery life can reach about 650 times.The comparable conventional formulation of life-span of battery prolongs about 200 times behind use the present invention.
Following table is the gravimetric specific energy contrast of above-mentioned 4 class batteries.
All kinds of battery weight specific energies of table 3
| Weight KG | 1HR capacity AH | HR capacity AH | HR capacity AH | HR capacity AH | Gravimetric specific energy VAH/KG | |
| A1 | 0.75 | 2.4 | 3.0 | 3.3 | 4.0 | 33.3 |
| A2 | 0.73 | 2.6 | 3.2 | 3.4 | 4.0 | 32.8 |
| A3 | 0.73 | 2.7 | 3.2 | 3.5 | 4.1 | 33.6 |
| A4 | 0.71 | 3.0 | 3.8 | 4.1 | 4.5 | 38.0 |
As seen, behind use the present invention, the gravimetric specific energy of battery is brought up to 38VAH/KG by original 32-34VAH/KG.
Experiment conclusion: the different specific weight with active material additives different in the anode lead plaster and active material carries out initial capacity, gravimetric specific energy, GB cycling life test to battery, draw as drawing a conclusion: along with the adding of short fiber, carbon raw and other active material in the prescription and add anisotropy graphite, carbon fiber simultaneously, battery initial capacity lead plaster battery more commonly used increases by 10～15%, GB cycle life can prolong about 200 times, and gravimetric specific energy is brought up to 38VAH/KG by original 32-34VAH/KG.
Embodiment 2
Take by weighing each composition as following weight percent:
1, lead powder 100%, 1.40g/cm
3Sulfuric acid content is 12% of a lead powder, and deionized water content is 11% of lead powder, and brown lead oxide content is 4.2% of lead powder, short fibre content is 0.06% of a lead powder, carbon fiber content is 0.08% of a lead powder, and the anisotropy content of graphite is 0.4% of a lead powder, and bismuth oxide content is 0.11% of lead powder.Lead powder, brown lead oxide, anisotropy graphite, short fiber, carbon fiber, bismuth oxide are mixed adding to be closed in the cream machine, stirred 5 minutes, it is even to add deionized water and stirring then apace, adds sulfuric acid more lentamente and stirs, be mixed with lead plaster and be used for making the 6V4AH battery, be labeled as B1.
2, lead powder 100%, 1.40g/cm3 sulfuric acid is 11% of lead powder content, deionized water is 10.5% of a lead powder content, brown lead oxide is 3.9% of a lead powder content, short fiber is 0.07% of a lead powder content, carbon fiber is 0.10% of a lead powder content, and anisotropy graphite is 0.2% of lead powder content, and bismuth oxide is 0.09% of a lead powder content.By above-mentioned technology, system 6V4AH battery is labeled as B2.
The prescription of Comparative Examples battery B3 is: lead powder 100%, brown lead oxide content are 14.2% of lead powder, and short fibre content is 0.018% of a lead powder, and deionized water content is that 18%, 98% bright sulfur acid content of lead powder is 4.2% of a lead powder.
Test all kinds of battery 20h and 3C capacity, compare examination as the battery initial capacity.The discharge data of above-mentioned battery averaged makes following table 4:
All kinds of battery initial performance of table 4 test data/h (min)
| B1 | B2 | B3 | |
| 20h leads | 22h12′ | 22h02′ | 20h |
| 3C | 8′59″ | 9′14″ | 8′13″ |
By data in the table 4 as can be seen: all kinds of batteries, the discharge test 20h that (GB/T19639.1-2005) require that can both be up to state standards leads discharge 20h and 7 minutes requirement of 3C discharge.And the battery capacity of present embodiment is apparently higher than Comparative Examples.
After the battery process initial capacity test passes, test the cycle life that goes up 3 class batteries in the table, the life test data of above-mentioned battery are averaged make following table according to the conventional batteries life test method.
Table 5 test battery GB cycle life data/time
| Battery types | B1 | B2 | B3 |
| The life-span number of times | 628 | 623 | 479 |
As can be seen from Table 5, B1 and B2 battery life cycle-index all reach more than 600, prolong about 150 than B3 control cell.Test the GB cycle life of two class batteries, the life-span correlation curve of B1 battery, B2 battery, B3 battery as shown in Figure 2.
Following table is the gravimetric specific energy contrast of above-mentioned all kinds of batteries.
All kinds of battery weight specific energies of table 6
| Weight KG | 1HR capacity AH | HR capacity AH | HR capacity AH | HR capacity AH | Gravimetric specific energy VAH/KG | |
| B1 | 0.72 | 3.1 | 3.5 | 3.85 | 4.4 | 36.6 |
| B2 | 0.70 | 2.9 | 3.6 | 3.9 | 4.4 | 37.7 |
| B3 | 0.72 | 2.7 | 3.2 | 3.5 | 4.0 | 33.3 |
As seen, behind use the present invention, the gravimetric specific energy of battery is brought up to 36-38VAH/KG by original 33VAH/KG.
Experiment conclusion: because the present invention has added additives such as short fiber, carbon fiber, anisotropy graphite, the proportioning of various compositions changes again, makes battery increase active material utilization, has reduced internal resistance, has increased capacity and charge-discharge performance.Make gravimetric specific energy bring up to 36-38VAH/KG, prolonged the useful life of battery especially by original 32-34VAH/KG.
Annotate: the GB of mentioning among the embodiment all is a pet-valve control sealed lead acid battery technical conditions national standard (standard No.: GBT 19639.1-2005)
The specific embodiment of the present invention not only is confined to the foregoing description, and the enforcement in every technical solutions according to the invention all belongs to protection scope of the present invention.
Claims (1)
1. a lead-acid accumulator anode diachylon comprises lead powder, 1.4g/cm
3Sulfuric acid, deionized water, brown lead oxide, short fiber, carbon fiber, anisotropy graphite and bismuth oxide is characterized in that: wherein each composition accounts for the percentage by weight of lead powder and is: lead powder 100%, 1.4g/cm
3Sulfuric acid 8～12%, deionized water 9～11%, brown lead oxide 3～4.2%, short fiber 0.05～0.06%, carbon fiber 0.10～0.15%, anisotropy graphite 0.2～0.4%, bismuth oxide 0.05～0.11%; Described deionized water resistivity is more than or equal to 0.6 Ω M; Described carbon fiber diameter is 0.1～0.9 μ m, and length is 4～6mm; Described staple length is 1～2mm, and fineness is 2Denier; Described anisotropy graphite fineness be 120 orders, residue on sieve less than 1, ash is less than 5, pH value is 6～7.
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