CN104577070A - High-temperature-resistant lead-carbon battery negative electrode material and manufacturing process thereof - Google Patents
High-temperature-resistant lead-carbon battery negative electrode material and manufacturing process thereof Download PDFInfo
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- CN104577070A CN104577070A CN201510037783.5A CN201510037783A CN104577070A CN 104577070 A CN104577070 A CN 104577070A CN 201510037783 A CN201510037783 A CN 201510037783A CN 104577070 A CN104577070 A CN 104577070A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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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
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Abstract
The invention provides a high-temperature-resistant lead-carbon battery negative electrode material and a manufacturing process thereof. The high-temperature-resistant lead-carbon battery negative electrode material is formed by mixing and stirring a first component and a second component, wherein the first component is prepared from the following ingredients in mass ratio: 28-36% of lead powder, 0.6-1.3% of sodium phosphate, 0.3-0.6% of graphite, 0.2-0.4% of stannous monosulphate and 61.7-69.7% of deionized water; and the second component is prepared from the following ingredients in mass ratio: 5-8% of PTFE, 12-18% of sodium carboxymethylcellulose, 6-10% of phosphoric acid and 64-72% of deionized water. By adopting the high-temperature-resistant lead-carbon battery negative electrode material and the manufacturing process thereof which are provided by the invention, the stability of the negative electrode material is improved, the negative electrode material has good high temperature resistance, 1C discharging capacity at high temperature is improved, and the discharge recycling life at high temperature is prolonged, so that the high-temperature-resistant lead-carbon battery negative electrode material is more adaptable to a severe environment, especially a high temperature environment, and the high-temperature-resistant lead-carbon battery negative electrode material is especially applicable to a solar battery.
Description
Technical field
The invention belongs to storage battery field, relate to a kind of high temperature resistant plumbous carbon secondary cell negative electrode material and manufacturing process thereof.
Background technology
Lead acid accumulator, refer to that electrode is made primarily of plumbous and oxide, electrolyte is a kind of storage battery of sulfuric acid solution.Lead acid accumulator relies on its advantage such as voltage stabilization, low price, obtains and applies comparatively widely.But lead acid accumulator shortcoming is also also comparatively obvious, such as: specific energy is on the low side, long, the easy thermal runaway of cycle life, battery heaviness, high-multiplying power discharge efficiency are low, low temperature easily lost efficacy on battery performance impact large (subzero 30 degree of low temperature lose charging and discharging ability), high temperature.
Especially seriously, the performance of lead acid accumulator is seriously close by temperature, and this seriously constrains performance boost and the range of application of lead acid accumulator.Because too high temperature can cause the increase of floating current, thus cause and overcharge the accumulative of electric current, make the shortening of cycle life of lead-acid accumulator.Verify bright factually, when ambient temperature is at 25 DEG C, temperature often raises 6 ~ 10 DEG C, and service life of lead accumulator shortens half.
And, when lead acid accumulator serviceability temperature is too high, the heat that lead acid accumulator produces in charge and discharge process is difficult to distribute, just cause that lead acid accumulator produces the aggravation of overheated, water loss, internal resistance increases, more generate heat, produce vicious circle, progressively develop into thermal runaway, cause waste lead-acid accumulators.Therefore, when embody rule, common lead acid accumulator is unsuitable for the environmental work more than 35 DEG C.
In some applications, above-mentioned shortcoming seriously can govern the application of lead acid accumulator, such as, and solar storage battery field.Solar storage battery is ' storage battery ' application in solar energy power generating, the domestic solar storage battery be widely used at present mainly lead acid accumulator.But solar storage battery must adapt to heavier adverse circumstances, especially hot environment, and as easy as rolling off a log damage or the inefficacy causing lead acid accumulator of hot environment.
Summary of the invention
The object of the present invention is to provide that one can work in high temperature environments, long service life, the high temperature resistant plumbous carbon secondary cell negative electrode material that capacity is high and manufacturing process thereof.
For achieving the above object, the invention provides a kind of high temperature resistant plumbous carbon secondary cell negative electrode material, this material is mixed together by the first component and second component;
Described first component is made up of according to quality proportioning following composition:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Described second component is made up of according to quality proportioning following composition:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%.
Furthermore, described first component is made up of according to quality proportioning following composition:
Lead powder 30 ~ 35%;
Sodium phosphate 0.8 ~ 1.2%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 65 ~ 68%;
Described second component is made up of according to quality proportioning following composition:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 15%;
Phosphoric acid 8 ~ 10%;
Deionized water 65 ~ 72%.
Wherein, described first component and second component mixed proportion are closed and are:
(7～8)：(1～1.2)。
Wherein, described material is mixed together by first component of 3050g and the second component of 1400g;
Described first component is made up of following composition: lead powder 1000g, sodium phosphate 25g, graphite 15g, stannous sulfate 10g, deionized water 2000g;
Described second component is made up of following composition: PTFE 100g, sodium carboxymethylcellulose 200g, phosphatase 11 00g, deionized water 1000g.
Wherein, in the aluminium powder of described first component, containing PbO 30 ~ 40% and PbO2 60 ~ 70%.
In addition, the present invention also provides a kind of manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material, comprises the following steps:
Step one, prepares the first component, lead powder, sodium phosphate, graphite and stannous sulfate is mixed, then adds deionized water and make solution, and heat a period of time to guarantee to be uniformly dispersed, make the first component; Wherein, in described first component, the quality proportioning of each composition is:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Step 2, prepares second component, PTFE, sodium carboxymethylcellulose and phosphoric acid is mixed, and adds deionized water and make viscous liquid, and heating is dissolved each other, and makes second component;
In described second component, the quality proportioning of each composition is:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%;
Step 3, by the first component and second component in (7 ~ 8): (1 ~ 1.2) ratio is mixed to get thick liquid, and stirs to guarantee to combine evenly between material;
Step 4, by the solution in step 3 through heat drying, and grind into powder;
Step 5, continues heat and stir by powder, can obtain high performance negative electrode lead carbon electrode material.
Wherein, in step one, during heated solution, heating-up temperature is 60 ~ 65 DEG C, and the heating time of dissolving each other is 3 ~ 4 hours; In step 2, during heated solution, heating-up temperature is 50 ~ 70 DEG C, and the heating time of dissolving each other is 1 hour.
Wherein, in step 3, agitating mode is that ultrasonic wave stirs, and mixing time is 2 hours.
Wherein, in step 4, the baking temperature of solution is 140 ~ 160 DEG C.
Wherein, in step 5, be 350 ~ 400 DEG C to the heating-up temperature of powder, heat treatment time is 4 ~ 6 hours.
The invention has the beneficial effects as follows: high temperature resistant plumbous carbon secondary cell negative electrode material provided by the invention and manufacturing process thereof, improve the stability of negative material, to detect after 40 cycle charge-discharges from pole plate without ruckbildung through 50 DEG C of high temperature 1C discharge cycles; The 1C discharge capacity of battery improves 15% ~ 30%; 50 DEG C of 1C discharge cycles life-spans of high temperature of battery improve 100-120%.Therefore, the plumbous carbon storage battery that high temperature resistant plumbous carbon secondary cell negative electrode material provided by the invention manufactures, there is good resistance to elevated temperatures, compared to traditional plumbous carbon storage battery, its 1C discharge capacity in high temperature environments and discharge cycles life-span are all improved, therefore more can adapt to adverse circumstances, especially hot environment, extremely be suitable as solar storage battery and use.
Accompanying drawing explanation
Fig. 1 is the process chart of the manufacturing process of the high temperature resistant plumbous carbon secondary cell negative electrode material of kind of the present invention.
Embodiment
High temperature resistant plumbous carbon secondary cell negative electrode material provided by the invention, this material is mixed together by the first component and second component;
First component is made up of according to quality proportioning following composition:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Second component is made up of according to quality proportioning following composition:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%.
Wherein, the first component and second component mixed proportion are closed and are: (7 ~ 8): (1 ~ 1.2).
In order to study its performance, by following concrete quality proportioning, prepare four parts of identical plumbous carbon secondary cell negative electrode materials, every part of negative material composed as follows:
Comprise first component of 3050g and the second component of 1400g; Wherein the first component is made up of following composition: lead powder 1000g, sodium phosphate 25g, graphite 15g, stannous sulfate 10g, deionized water 2000g; Second component is made up of following composition: PTFE 100g, sodium carboxymethylcellulose 200g, phosphatase 11 00g, deionized water 1000g.
The plumbous carbon storage battery that utilized above-mentioned negative material to prepare, is respectively 1# battery, 2# battery, 3# battery and 4# battery.Above-mentioned four Battery packs and traditional lead acid batteries one coexist under 50 DEG C of high temperature, do high temperature 1C discharge test, and its experimental data is respectively as shown in table one to four.
1# battery, high temperature 1C discharges correction data, as shown in Table 1.
Table one
2# battery, high temperature 1C discharges correction data, as shown in Table 2.
Table two
3# battery, high temperature 1C discharges correction data, as shown in Table 3.
Table three
4# battery, high temperature 1C discharges correction data, as shown in Table 4.
Table four
As can be seen from the data of table one to four, high temperature resistant plumbous carbon secondary cell negative electrode material provided by the invention, improves the stability of negative material, to detect after 40 cycle charge-discharges from pole plate without ruckbildung through 50 DEG C of high temperature 1C discharge cycles; The 1C discharge capacity of battery improves 15% ~ 30%; 50 DEG C of 1C discharge cycles life-spans of high temperature of battery improve 100-120%.Therefore, the plumbous carbon storage battery that high temperature resistant plumbous carbon secondary cell negative electrode material provided by the invention manufactures, there is good resistance to elevated temperatures, compared to traditional plumbous carbon storage battery, its 1C discharge capacity in high temperature environments and discharge cycles life-span are all improved, therefore more can adapt to adverse circumstances, especially hot environment, extremely be suitable as solar storage battery and use.
High-temperature behavior is good, also can ensure normal service life without air conditioner facility occasion, the communication spare power supplies used under being especially suitable as hot environment; Battery capacity is improved, and adds the utilance of active material, reduces battery dehydration in high temperature environments, decreases battery thermal runaway phenomenon.
In the present embodiment, in the aluminium powder of the first component, containing PbO 30 ~ 40% and PbO2 60 ~ 70%.Experimental data proves, meets the aluminium powder of above-mentioned condition, the most applicable plumbous carbon secondary cell negative electrode material of the present invention, and its performance of the plumbous carbon storage battery of production is best.Certainly, this is only a specific embodiment of the present invention, and the concrete composition of aluminium powder of the present invention is not limited in this.
The present invention also provides a kind of manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material, comprises the following steps:
Step one, prepares the first component, lead powder, sodium phosphate, graphite and stannous sulfate is mixed, then adds deionized water and make solution, dissolve each other 3 ~ 4 hours, to guarantee to be uniformly dispersed with the heating temperatures of 60 ~ 65 DEG C; Wherein, in the first component, the quality proportioning of each composition is:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Step 2, prepares second component, PTFE, sodium carboxymethylcellulose and phosphoric acid is mixed, and adds deionized water and make viscous liquid, dissolve each other 1 hour, make second component with the heating temperatures of 50 ~ 70 DEG C; Wherein, in second component, the quality proportioning of each composition is:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%;
Step 3, by the first component and second component in (7 ~ 8): (1 ~ 1.2) ratio is mixed to get thick liquid, and ultrasonic wave stirs 2 hours, guarantees to combine evenly between material;
Step 4, by the solution in step 3 through 140 ~ 160 DEG C of heat dryings, and grind into powder;
Step 5,350 ~ 400 DEG C are stirred also heat treatment and, after 4 ~ 6 hours, can obtain high performance negative electrode lead carbon electrode material.
Through experimental verification, the high temperature resistant plumbous carbon secondary cell negative electrode material utilizing said method to manufacture, stability is greatly improved, the plumbous carbon storage battery utilizing obtained negative material to manufacture, has good resistance to elevated temperatures, compared to traditional plumbous carbon storage battery, its 1C discharge capacity in high temperature environments and discharge cycles life-span are all improved, therefore more can adapt to adverse circumstances, especially hot environment, extremely be suitable as solar storage battery and use.
These are only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a high temperature resistant plumbous carbon secondary cell negative electrode material, it is characterized in that, this material is mixed together by the first component and second component;
Described first component is made up of according to quality proportioning following composition:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Described second component is made up of according to quality proportioning following composition:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%.
2. high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 1, it is characterized in that, described first component is made up of according to quality proportioning following composition:
Lead powder 30 ~ 35%;
Sodium phosphate 0.8 ~ 1.2%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 65 ~ 68%;
Described second component is made up of according to quality proportioning following composition:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 15%;
Phosphoric acid 8 ~ 10%;
Deionized water 65 ~ 72%.
3. high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 1 and 2, is characterized in that, described first component and second component mixed proportion are closed and be:
(7～8)：(1～1.2)。
4. high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 3, is characterized in that, described material is mixed together by first component of 3050g and the second component of 1400g;
Described first component is made up of following composition: lead powder 1000g, sodium phosphate 25g, graphite 15g, stannous sulfate 10g, deionized water 2000g;
Described second component is made up of following composition: PTFE 100g, sodium carboxymethylcellulose 200g, phosphatase 11 00g, deionized water 1000g.
5. the high temperature resistant plumbous carbon secondary cell negative electrode material according to any one of Claims 1 to 4, is characterized in that, in the aluminium powder of described first component, containing PbO 30 ~ 40% and PbO
260 ~ 70%.
6. a manufacturing process for high temperature resistant plumbous carbon secondary cell negative electrode material, is characterized in that, comprise the following steps:
Step one, prepares the first component, lead powder, sodium phosphate, graphite and stannous sulfate is mixed, then adds deionized water and make solution, and heat a period of time to guarantee to be uniformly dispersed, make the first component; Wherein, in described first component, the quality proportioning of each composition is:
Lead powder 28 ~ 36%;
Sodium phosphate 0.6 ~ 1.3%;
Graphite 0.3 ~ 0.6%;
Stannous sulfate 0.2 ~ 0.4%;
Deionized water 61.7 ~ 69.7%;
Step 2, prepares second component, PTFE, sodium carboxymethylcellulose and phosphoric acid is mixed, and adds deionized water and make viscous liquid, and heating is dissolved each other, and makes second component;
In described second component, the quality proportioning of each composition is:
PTFE 5～8%；
Sodium carboxymethylcellulose 12 ~ 18%;
Phosphoric acid 6 ~ 10%;
Deionized water 64 ~ 72%;
Step 3, by the first component and second component in (7 ~ 8): (1 ~ 1.2) ratio is mixed to get thick liquid, and stirs to guarantee to combine evenly between material;
Step 4, by the solution in step 3 through heat drying, and grind into powder;
Step 5, continues heat and stir by powder, can obtain high performance negative electrode lead carbon electrode material.
7. the manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 6, is characterized in that, in step one, during heated solution, heating-up temperature is 60 ~ 65 DEG C, and the heating time of dissolving each other is 3 ~ 4 hours; In step 2, during heated solution, heating-up temperature is 50 ~ 70 DEG C, and the heating time of dissolving each other is 1 hour.
8. the manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 6, is characterized in that, in step 3, agitating mode is that ultrasonic wave stirs, and mixing time is 2 hours.
9. the manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 6, is characterized in that, in step 4, the baking temperature of solution is 140 ~ 160 DEG C.
10. the manufacturing process of high temperature resistant plumbous carbon secondary cell negative electrode material according to claim 6, is characterized in that, in step 5, be 350 ~ 400 DEG C to the heating-up temperature of powder, heat treatment time is 4 ~ 6 hours.
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