CN1331257C - Positive lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof - Google Patents
Positive lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof Download PDFInfo
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- CN1331257C CN1331257C CNB2005100129140A CN200510012914A CN1331257C CN 1331257 C CN1331257 C CN 1331257C CN B2005100129140 A CNB2005100129140 A CN B2005100129140A CN 200510012914 A CN200510012914 A CN 200510012914A CN 1331257 C CN1331257 C CN 1331257C
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Abstract
The present invention relates to anode lead plaster for a valve-controlled sealed lead acid accumulator used for starting a vehicle and a preparation method, which belongs to the technical field of the accumulators. The present invention is used for solving the problem of the charging capacity of accumulators under the low voltage states. The present invention has the improvement that solid raw materials of lead plaster are composed of the materials of 100kg of lead powder, 0.05 to 0.06kg of fiber and 0.1 to 0.3kg of high pure natural graphite powder by weight unit. The present invention selects electricity conductive anode additive with oxidation resistance, the crystal structures of anode active materials are improved and can be maintained for a long lifetime, the chargeable capability of the accumulator under the low voltage states is improved, and anode plates can always operate in a state that the anode plates can not accumulate loss electricity in the operational process of the lifetime. The manufacturing process for the lead plaster in high temperature of the present invention strengthens the skeleton structures of anode active materials. The test data indicates that the accumulator made of the anode lead plaster of the present invention is adopted, the performance indexes of a major technique can be achieved and exceed the standard requirements, and the requirements of automobile users are met.
Description
Technical field
The present invention relates to a kind of accumulator material and preparation method, particularly automobile start belongs to the battery technology field with positive lead cream of valve-controlled sealed plumbous acid accumulator and preparation method thereof.
Background technology
Along with the develop rapidly of auto industry, more and more higher to the performance requirement of lead-acid accumulator. Valve-regulated sealed battery is as the high-end product of lead-acid accumulator, and along with nearly 20 years going deep into of using and study, its actual serviceability, stability, life characteristic have had significant progress, and application is more extensive. The automobile of at present abroad doing back-up power source with valve control battery is produced in batches, uses the 42V system automobile of valve control sealed battery (starting, illumination, igniting, energy storage, auxiliary power with) also to emerge such as Japanese Toyota, Honda. Valve-control sealed lead acid battery with the common ground of general pregnant solution type lead acid accumulator is: the groundwork commercial weight of bis sulfonate theory is identical. Difference is: 1. valve control battery will be worked under lower charging voltage; 2. for reducing the gassing dehydration, based on the oxygen cycle principle, valve control sealed battery adopts barren liquor type design (electrolyte is adsorbed in AGM dividing plate or the colloid); 3. because electrolyte content is few, battery must use higher density of electrolyte (〉=1.300g/cm3)。
When lead-acid accumulator was produced at present, formula of positive lead paste was: lead powder, fiber, dilute sulfuric acid and water. Power density and the energy density of lead-acid accumulator are lower, because the density of lead and compound thereof is larger on the one hand, because the utilization rate of its active material is low on the other hand, especially positive electrode active material utilization is low, and the life-span of battery is subject to positive pole more, therefore the insider is devoted to research to positive active material always in recent years, in the hope of improving its utilization rate and extending battery life.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of above-mentioned prior art and provide a kind of automobile start with positive lead cream of valve-controlled sealed plumbous acid accumulator and preparation method thereof, thereby improve the crystalline texture of positive active material, even so that more even work of anode diachylon reaction still has good charging to accept performance under lower charging voltage.
The alleged problem of the present invention is solved by following technical scheme:
A kind of automobile start positive lead cream of valve-controlled sealed plumbous acid accumulator, its special feature is: described lead plaster solid material is comprised of the material of following weight unit's: lead powder 100, fiber 0.05～0.06, high-purity natural graphite powder 0.1～0.3.
Above-mentioned automobile start positive lead cream of valve-controlled sealed plumbous acid accumulator, described high-purity natural graphite powder are that natural flaky graphite is removed impurity through screening, again through washing, separation, drying, obtain required purity, its purity 〉=99.85%; Ignition residue≤0.15%; At least 90% grain diameter is between 30 μ m～65 μ m.
Above-mentioned automobile start positive lead cream of valve-controlled sealed plumbous acid accumulator, PbO content is 75-85% in the described lead powder.
The above-mentioned automobile start preparation method of positive lead cream of valve-controlled sealed plumbous acid accumulator, it is undertaken by following operation:
A. prepare burden: take by weighing each raw material by above-mentioned lead plaster solid material proportioning;
B. be dry mixed: above-mentioned lead plaster solid material is put into paste mixing machine be dry mixed;
C. wet mixing: the pure water that adds raw material weight 10～12% stirs;
D. drench acid: while stirring take shape spray add raw material weight 8～10%, density as 1.40g/cm3Sulfuric acid solution, and the cream temperature keeps 10～20min in the time of 75～85 ℃, cooling goes out the cream temperature and is lower than 45 ℃.
The present invention is directed to automobile start and move under lower charging voltage with valve control battery, still need have good charging and accept performance and long-life requirement and design. It selects sludge proof conduction anode additive, the crystalline texture of having improved positive active material also can be maintained in the long life-span, positive plate improved the chargeable ability of battery at low-voltage (under the partial state of charge), so that can not add up the power shortage operation all the time in the life-span running. The high temperature lead plaster manufacture craft that the present invention adopts has been strengthened the skeleton structure of positive active material. Test data shows, carry out Performance Detection according to current international advanced VW75073 automobile start with the battery standard, the battery that adopts anode diachylon of the present invention to make, the basic mechanical design feature index can meet and exceed standard-required fully, satisfies the requirement of user vehicle.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (amplifying 500 times) of conductive network in the active material.
Black bar among the figure is that lead plaster adds the material fiber; Central authorities radial material be 3BS the 4BS crystallization, crystallization central authorities are the aggregation of carbon (C); This network-like structure is in the lead plaster distributed throughout, and network integration is tight, and the larger space of middle formation is conducive to the diffusion of acid solution in the battery reaction, and the carbon of central authorities then provides the electronic conduction passage. Scheme beyond the central radial material for the more tiny random 3BS that forms in the lead plaster solidification process 4BS the Pb crystallization.
The specific embodiment
The present invention selects anode additive to join in the positive active material and leads and porosity with the electricity that improves positive active material according to the characteristics that automobile start is high with the valve-control storage battery density of electrolyte, charged electrical forces down; Improve between active material and the grid adhesion and PbO2Adhesion between the particle makes positive active material that higher charging conversion ratio can be arranged, and improves operating active material utilization. Concrete grammar is to add the novel anode additive in anode diachylon: the high-purity natural graphite powder, its suitable addition is 0.1～0.3% of lead powder weight. So-called high-purity natural graphite powder has high dispersion, the inadherent characteristic of determining. Native graphite can be divided into compact massive graphite and flaky graphite by its crystal habit. Adopt natural flaky graphite among the present invention, its screening is removed impurity to obtain higher high-carbon (91～99%) graphite of phosphorus content, again through washing, separation, drying, obtain the graphite powder of required purity. This graphite powder has been preserved the sclay texture of the densification of former graphite, purity 〉=99.85%, and ignition residue≤0.15%, at least 90% grain diameter is between 30 μ m～65 μ m. Its resistance to oxidation is stronger, resistance is less, electric conductivity is stronger. Use it in the anode diachylon and can improve formation efficiency, it has the distribution of particle sizes close with lead powder, but high degree of dispersion makes to change into and to discharge and recharge reaction more even in active material in lead plaster manufacturing process. Show that through experimental observation product of the present invention can form the conductive network (referring to accompanying drawing 1) take C as core in active material, improve the crystalline structure of active material, has improved the efficiency for charge-discharge in the battery operation process. In addition, adopt paste mixing at high temperature technique can make lead plaster form more 4BS crystallization (four basic lead sulphates), strengthen the skeleton structure of positive active material.
Following table is that the automobile start that adopts lead plaster of the present invention to make is tested the technical indicator (take the 60Ah battery as example) that reaches with valve-control sealed lead acid battery:
| Sequence number | Interventions Requested | Test method (with reference to VW75073) | Unit | Adopt the automobile start valve-control sealed lead acid battery of this present invention lead plaster | The valve control battery that directly adopts general rich solution maintenance-free lead accumulator lead plaster technique to make | General rich solution maintenance-free lead accumulator |
| 1 | Capacity | Under 25 ± 2 ℃ of environment temperatures, battery 9.6A is discharged to 10.5V, capacity 〉=48Ah | Ah | 53 | 50 | 52 |
| 2 | Cold-starting (18 ℃) | Complete fully charged battery kept 20 hours in-18 ± 1 ℃ of environment at least, reach-18 ℃ fully to internal temperature of battery after, the 480A 10s that discharges, voltage 〉=75V, stop 10s after, the 280A discharge, 20s 〉=9V is discharged to time 〉=133s of 6.0V | V 10s V 20s s | 8.87 9.98 201 | 8.58 9.76 182 | 8.83 9.92 188 |
| 3 | Capacity | With 1 | Ah | 50 | 44 | 50 |
| 4 | Cold-starting (18 ℃) | With 2 | V 10s V 10s s | 8.47 9.69 190 | 8.53 9.7 179 | 8.75 9.86 173 |
| 5 | Current drain (charging is accepted) | With the 9.6A discharge, the time is half of 1,3 discharge time, then enters 0 ℃ of cryogenic box 24h, again with the 14.4V charging, and charging current value 〉=15A of record 10min | A | 15.7 | 14 | 15 |
| 6 | 17.5% life-span | In 27 ± 2 ℃ water-bath, 1. with the 12A 2.5h that discharges, battery tension≤10V stops; 2. use constant voltage 14.4V, the current limliting 21A 40min that charges; With the 21A 30min that discharges, charge and discharge circulation 85 times, battery tension≤10V stops 3. using constant voltage 15V, the current limliting 6A 18h that charges; 4. carrying out capacity test by article one then charges. 1.～4. consist of a unit, carry out cold-starting according to second behind every unit, the 480A 10s that discharges, voltage 〉=6V, stop 10s after, 280A discharge, 20s 〉=7.2V. At least 6 unit. | 12 | 6 | 6 | |
| 7 | 50% life-span | In 40 ± 2 ℃ water-bath, 1. with the 15A 2h that discharges; 2. use constant voltage 16V, the current limliting 15A 5h that charges; Above-mentionedly 1., 2. consist of a circulation, when discharge voltage during less than 10.0V, end-of-life. At least 120 times | 360 | 60 | 120 | |
| 8 | Confined reaction efficient | Test 〉=90% with reference to 7.8 of JIS C8702-1-1998 | ％ | 98％ | / |
Can be found out that by data in the table automobile start that adopts the present invention to make has suitable cold-starting ability and good charging performance with valve-control sealed lead acid battery and general rich solution maintenance-free lead accumulator, and has obtained the longer life-span. But the valve control battery that directly adopts general rich solution maintenance-free lead accumulator lead plaster technique to make because positive/negative plate all is difficult to full charge under low-voltage, causes the life-span premature termination of battery.
Several instantiations below are provided:
Embodiment 1: be that 75%～85% lead powder adds in the paste mixing machine with 100kgPbO content, add simultaneously the fiber of 0.05kg, the high-purity natural graphite powder of 0.3kg, above-mentioned material stirring is even, then add purifying waste water of 10kg, after hygrometric state mixed, drenching density fast was 1.400g/cm3The sulfuric acid solution 10kg of (25 ℃), and control and 75 ℃～85 ℃ of cream temperature in the process processed, keep 10～20min question response evenly after, take cooling measure, temperature drops to below 45 ℃, can go out the cream use.
Embodiment 2: be that 75%～85% lead powder adds in the paste mixing machine with 100kg PbO content, add simultaneously the fiber of 0.06kg, the high-purity natural graphite powder of 0.1kg, above-mentioned material stirring is even, then add purifying waste water of 12kg, after hygrometric state mixed, drenching density fast was 1.400g/cm3The sulfuric acid solution 8kg of (25 ℃), and control and 75 ℃～85 ℃ of cream temperature in the process processed, keep 10～20min reaction evenly after, take cooling measure, temperature drops to below 45 ℃, can go out the cream use.
Embodiment 3: be that 75%～85% lead powder adds in the paste mixing machine with 100kg PbO content, add simultaneously the fiber of 0.055kg, the high-purity natural graphite powder of 0.2kg, above-mentioned material stirring is even, then add purifying waste water of 11kg, after hygrometric state mixed, drenching density fast was 1.400g/cm3The sulfuric acid solution 9kg of (25 ℃), and control and 75 ℃～85 ℃ of cream temperature in the process processed, keep 10～20min reaction evenly after, take cooling measure, temperature drops to below 45 ℃, can go out the cream use.
Used high purity graphite powder is that natural flaky graphite is removed impurity through screening in the above-described embodiments, again through washing, separation, drying, obtains the graphite powder of required purity. Its purity 〉=99.85%; Ignition residue≤0.15%; At least 90% grain diameter is between 30 μ m～65 μ m.
The anode diachylon of as stated above preparation is coated on the grid, solidifies 24h through 40 ℃, 98%RH, produce and just give birth to plate through 70 ℃, the dry 24h of 20%RH again, the negative plate of giving birth to can adopt automobile start valve control sealed battery cathode lead plaster and the manufacturing of pole plate manufacture technology.
Through pole plate change into, behind dry, minute plate, pole plate coats the AGM dividing plate, the private casing of packing into is sealed to the automobile start valve control sealed battery.
Fiber described in the present invention is polyester fiber commonly used in the battery industry.
Claims (3)
1. automobile start positive lead cream of valve-controlled sealed plumbous acid accumulator, it is characterized in that: described lead plaster solid material is comprised of the material of following weight unit's: lead powder 100, polyester fiber 0.05～0.06, high-purity natural graphite powder 0.1～0.3; Described high-purity natural graphite powder is that natural flaky graphite is removed impurity through screening, again through washing, separation, drying, obtains required purity, its purity 〉=99.85%; Ignition residue≤0.15%; The grain diameter of sand 90% is between 30 μ m～65 μ m.
2. automobile start positive lead cream of valve-controlled sealed plumbous acid accumulator according to claim 1, it is characterized in that: PbO content is 75-85% in the described lead powder.
3. automobile start according to claim 1 and 2 is with the preparation method of positive lead cream of valve-controlled sealed plumbous acid accumulator, and it is characterized in that: it is undertaken by following operation:
A. prepare burden: take by weighing each raw material by above-mentioned lead plaster solid material proportioning;
B. be dry mixed: above-mentioned lead plaster solid material is put into paste mixing machine be dry mixed;
C. wet mixing: the pure water that adds raw material weight 10～12% stirs;
D. drench acid: while stirring take shape spray add people's raw material weight 8～10%, density as 1.40g/cm3Sulfuric acid solution, and the cream temperature keeps 10～20min in the time of 75～85 ℃, cooling goes out the cream temperature and is lower than 45 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100129140A CN1331257C (en) | 2005-10-14 | 2005-10-14 | Positive lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100129140A CN1331257C (en) | 2005-10-14 | 2005-10-14 | Positive lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof |
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| CN1747204A CN1747204A (en) | 2006-03-15 |
| CN1331257C true CN1331257C (en) | 2007-08-08 |
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| CNB2005100129140A Expired - Fee Related CN1331257C (en) | 2005-10-14 | 2005-10-14 | Positive lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285201B (en) * | 2008-04-12 | 2010-06-02 | 姚贤章 | Process for electrolyzing and producing manganese anode sheet |
| CN101924210A (en) * | 2010-07-30 | 2010-12-22 | 风帆股份有限公司 | Anode lead paste with high utilization rate of active substances of lead-acid battery and preparation method thereof |
| CN102074695A (en) * | 2010-12-21 | 2011-05-25 | 江苏永达电源股份有限公司 | High-temperature paste mixing process for prolonging cycle life of battery |
| CN102244248A (en) * | 2011-06-10 | 2011-11-16 | 江苏双登集团有限公司 | Positive plate of lead storage battery for electric bicycle |
| CN105552364B (en) * | 2016-01-07 | 2017-12-29 | 超威电源有限公司 | A kind of lead acid battery positive electrode exempts to solidify the preparation method of lead plaster |
| CN110190204A (en) * | 2019-05-15 | 2019-08-30 | 佛山赛能新能源有限公司 | A kind of production method of hot-resistant valve control lead-acid battery and its positive plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152803A (en) * | 1995-12-22 | 1997-06-25 | 陈有孝 | Large fully-closed maintenance-free lead-acid accumulator for low-temp. starting |
| US6083641A (en) * | 1998-05-08 | 2000-07-04 | The United States Of America As Represented By The United States Department Of Energy | Titanium carbide bipolar plate for electrochemical devices |
| CN1391303A (en) * | 2001-06-12 | 2003-01-15 | 冯月生 | Environment protection type pressure-resistant accumulator suitable for deep sea job |
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2005
- 2005-10-14 CN CNB2005100129140A patent/CN1331257C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152803A (en) * | 1995-12-22 | 1997-06-25 | 陈有孝 | Large fully-closed maintenance-free lead-acid accumulator for low-temp. starting |
| US6083641A (en) * | 1998-05-08 | 2000-07-04 | The United States Of America As Represented By The United States Department Of Energy | Titanium carbide bipolar plate for electrochemical devices |
| CN1391303A (en) * | 2001-06-12 | 2003-01-15 | 冯月生 | Environment protection type pressure-resistant accumulator suitable for deep sea job |
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