CN111403737A - Negative electrode additive composition for lead-acid battery and preparation method thereof - Google Patents
Negative electrode additive composition for lead-acid battery and preparation method thereof Download PDFInfo
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- CN111403737A CN111403737A CN202010177658.5A CN202010177658A CN111403737A CN 111403737 A CN111403737 A CN 111403737A CN 202010177658 A CN202010177658 A CN 202010177658A CN 111403737 A CN111403737 A CN 111403737A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of battery additive preparation, and particularly discloses a negative electrode additive composition for a lead-acid battery and a preparation method thereof. The negative electrode additive composition comprises the following components in parts by weight: 1-5 parts of sodium lignosulphonate; 1-5 parts of humic acid; 1-5 parts of carbon black; 3-10 parts of barium sulfate. The negative electrode additive composition can greatly improve the charge acceptance of the lead-acid battery.
Description
Technical Field
The invention relates to the technical field of battery additive preparation, in particular to a negative electrode additive composition for a lead-acid battery and a preparation method thereof.
Background
The power battery is a power supply for providing power for tools such as an electric automobile and the like; the lead-acid storage battery is one of the commonly used power batteries, and comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The negative electrode of the lead-acid battery is a lead plate filled with spongy lead, the negative electrode material of the lead-acid battery generally contains components such as lead powder, sodium lignosulfonate (dispersing agent), barium sulfate (nucleating agent), carbon black (conductive material) and the like, the components, water, sulfuric acid and the like are added into a paste mixer (horizontal low-speed stirring mixer) for neutralization to form a negative electrode material at one time, and then the negative electrode material is coated to form a negative electrode green plate. Sodium lignosulfonate and carbon black materials in the negative electrode additive have an important influence on the charging performance of the lead-acid storage battery. Therefore, it is important to provide a negative electrode additive composition capable of improving the charging performance of a lead-acid battery.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a negative electrode additive composition for a lead-acid battery; the negative electrode additive composition can greatly improve the charge acceptance of the lead-acid battery.
The technical problem to be solved by the invention is realized by the following technical scheme:
a negative electrode additive composition for a lead-acid battery comprises the following components in parts by weight:
1-5 parts of sodium lignosulphonate; 1-5 parts of humic acid; 1-5 parts of carbon black; 3-10 parts of barium sulfate.
Preferably, the negative electrode additive composition for lead-acid batteries comprises the following components in parts by weight:
1-3 parts of sodium lignosulphonate; 1-3 parts of humic acid; 1-3 parts of carbon black; 3-8 parts of barium sulfate.
Most preferably, the negative electrode additive composition for lead-acid batteries comprises the following components in parts by weight:
1 part of sodium lignosulphonate; 1 part of humic acid; 1 part of carbon black; 5 parts of barium sulfate.
Preferably, the sodium lignosulfonate is selected from sodium lignosulfonate addina-K.
Preferably, the carbon black is selected from carbon black R425P.
Sodium lignosulfonate addina-K and carbon black R425P are available from angstromada chemical company, guangzhou.
The inventor researches and discovers that the selection of sodium lignosulfonate and carbon black in the negative electrode additive has an important influence on the charging performance of the lead-acid storage battery, and when the sodium lignosulfonate is selected from sodium lignosulfonate addina-K and the carbon black is selected from carbon black R425P, the charging acceptance of the lead-acid storage battery can be greatly improved compared with the other sodium lignosulfonate and the carbon black.
The invention also provides a preparation method of the negative electrode additive composition for the lead-acid battery, which comprises the following steps:
(1) mixing sodium lignosulphonate, humic acid, carbon black and barium sulfate to obtain a mixture;
(2) and performing ball milling on the mixture to obtain the negative electrode additive composition for the lead-acid battery.
Preferably, the mixing in step (1) is carried out in a mixer; and (3) performing ball milling in a ball mill in the step (2).
Preferably, the grinding medium in the ball mill is selected to have a density of 2.7-9 g/cm3The metal balls and/or metal oxide ceramic balls of (a); the volume filling rate of the grinding medium in the ball mill is 20-60%.
Further preferably, the metal ball is selected from 304 stainless steel balls; the metal oxide ceramic ball is selected from a zirconium dioxide ceramic ball or an aluminum oxide ceramic ball.
Preferably, the grinding media in the ball mill are graded by metal balls and/or metal oxide ceramic balls with three sizes; respectively are metal balls or metal oxide ceramic balls with the diameter of 2-15 mm; metal balls or metal oxide ceramic balls with the diameter of 15-50 mm; metal balls or metal oxide ceramic balls with a diameter of 50-100 mm.
More preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-50: 1-50: 1 to 50.
More preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-5: 1-5: 1 to 5.
Most preferably, the grinding media in the ball mill are graded by selecting metal balls and/or metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 2-15 mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 15-50 mm; alumina ceramic balls with the diameter of 50-100 mm; the weight ratio of the 304 stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 3-5: 1-2: 1.
further research by the inventors shows that the preparation method of the negative electrode additive composition also has an important influence on the charging performance of the lead-acid storage battery. The negative electrode additive composition obtained by carrying out the step ball milling on the negative electrode additive composition under the conditions further improves the charging receiving capacity of the lead-acid storage battery. The graded ball milling is a key technology, and compared with a negative electrode additive composition obtained by a general mixing mode and non-graded ball milling, the charging acceptance of the lead-acid storage battery is improved more remarkably.
Detailed Description
The present invention is further explained below with reference to specific examples, but the scope of protection of the present invention is not limited to the specific examples.
Example 1 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black R425P 1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
example 2 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black R425P 1 parts; and 3 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 60min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 30 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 2mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 15 mm; alumina ceramic balls with the diameter of 50 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 10: 5: 3.
example 3 preparation of negative electrode additive composition
The raw material ratio is as follows: 3 parts of sodium lignosulphonate addiNam-K; 2 parts of humic acid; carbon black R425P 3 parts; 8 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 60min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 60 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 5mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 50 mm; alumina ceramic balls with the diameter of 100 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 20: 10: 1.
comparative example 1 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-P; 1 part of humic acid; carbon black R425P 1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-P, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 1 differs from example 1 in that sodium lignosulfonate addina-P is substituted for sodium lignosulfonate addina-K.
Comparative example 2 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black Raven P5UP1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black Raven P5UP and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 2 differs from example 1 in that carbon black Raven P5UP is used in place of carbon black R425P.
Comparative example 3 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-P; 1 part of humic acid; carbon black Raven P5UP1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulphonate addina-P, humic acid, carbon black Raven P5UP and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 3 differs from example 1 in that sodium lignosulfonate addina-P is substituted for sodium lignosulfonate addina-K; carbon black R425P was replaced by carbon black Raven P5 UP.
Comparative example 4 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black R425P 1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) and mixing the mixture in a high-speed mixer for 60min to obtain the negative electrode additive composition.
Comparative example 4 is different from example 1 in that high-speed mixer is used instead of ball mill for ball milling in step (2).
Comparative example 5 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black R425P 1 parts; 5 parts of barium sulfate.
(1) Mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with two sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; a 304 stainless steel ball with the diameter of 25 mm; the weight ratio of the 10mm 304 stainless steel ball to the 25mm 304 stainless steel ball is 2: 1.
comparative example 5 differs from example 1 in that only 2 sizes of ball milling media were used in step (2) and 3 sizes were used in example 1.
Comparative example 6 preparation of negative electrode additive composition
The raw material ratio is as follows: 1 part of sodium lignosulphonate addiNam-K; 1 part of humic acid; carbon black R425P 1 parts; 5 parts of barium sulfate.
The preparation method comprises the following steps:
(1) mixing sodium lignosulfonate addina-K, humic acid, carbon black R425P and barium sulfate in a horizontal coulter mixer for 30min to obtain a mixture;
(2) ball-milling the mixture in a ball mill for 30min to obtain a negative electrode additive composition; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; a 304 stainless steel ball with the diameter of 20 mm; alumina ceramic balls with the diameter of 40 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 6 differs from example 1 in that the ball milling media in step (2) are different.
Examples of the experiments
Mixing the negative electrode additive composition prepared in the examples 1-3 and the comparative examples 1-6 with lead powder, dilute sulfuric acid and water, adding the mixture into a paste mixing machine for neutralizing paste to obtain a negative electrode material of the power battery, and then respectively coating the negative electrode material of the power battery to prepare a negative electrode plate of the power battery; then assembled into a 12V20Ah power battery of the electric bicycle, and the electric bicycle is tested according to the standard GB22199-2008Charging acceptance of power battery (charging current Ica and C)2Ratio/10), the results are shown in table 1.
TABLE 1 test results of the charge acceptance of power batteries
| Charge acceptance capability | |
| Example 1 negative electrode additive composition | 3.8 |
| Example 2 negative electrode additive composition | 3.5 |
| Example 3 negative electrode additive composition | 3.6 |
| Comparative example 1 negative electrode additive composition | 2.7 |
| Comparative example 2 negative electrode additive composition | 2.6 |
| Comparative example 3 negative electrode additive composition | 2.3 |
| Comparative example 4 negative electrode additive composition | 2.5 |
| Comparative example 5 negative electrode additive composition | 2.7 |
| Comparative example 6 negative electrode additive composition | 2.9 |
As can be seen from the charge acceptance of the batteries obtained by using the negative electrode additive compositions of examples 1-3, the charge acceptance is more than 3.5 and is far higher than 2.0 specified by the standard; this demonstrates that the charge acceptance of lead acid batteries can be greatly improved using the negative electrode additive composition of the present invention.
As can be seen from the charge acceptance of the batteries obtained using the negative electrode additive compositions of comparative examples 1 to 3, it is much smaller than that of the battery obtained using the negative electrode additive composition of example 1. This demonstrates that sodium lignosulfonate and carbon black have a significant effect on the charge acceptance of lead acid batteries. In the negative electrode additive composition, sodium lignosulfonate addina-K and carbon black R425P must be simultaneously adopted to greatly improve the charge acceptance of the lead-acid storage battery. And the charge acceptance of the lead-acid storage battery cannot be greatly improved by selecting other sodium lignosulfonate and carbon black.
As can be seen from the charge acceptance of the batteries obtained using the negative electrode additive compositions of comparative examples 4 to 6, it is much smaller than that of the battery obtained using the negative electrode additive composition of example 1. This is to be understood as meaning that,
the preparation method of the negative electrode additive composition also has important influence on the charging performance of the lead-acid storage battery. The charge acceptance of the negative electrode additive composition on the lead-acid storage battery can be further improved only by the negative electrode additive composition obtained by carrying out graded ball milling on the negative electrode additive composition under the condition of the invention. Under other conditions, the charge acceptance of the lead-acid storage battery is not obviously improved.
Claims (9)
1. The negative electrode additive composition for the lead-acid battery is characterized by comprising the following components in parts by weight:
1-5 parts of sodium lignosulphonate; 1-5 parts of humic acid; 1-5 parts of carbon black; 3-10 parts of barium sulfate.
2. The negative electrode additive composition for a lead-acid battery according to claim 1, characterized by comprising the following components in parts by weight:
1-3 parts of sodium lignosulphonate; 1-3 parts of humic acid; 1-3 parts of carbon black; 3-8 parts of barium sulfate.
3. The negative electrode additive composition for a lead-acid battery according to claim 1, characterized by comprising the following components in parts by weight:
1 part of sodium lignosulphonate; 1 part of humic acid; 1 part of carbon black; 5 parts of barium sulfate.
4. The negative electrode additive composition for lead acid batteries according to claim 1, wherein said sodium lignosulfonate is selected from sodium lignosulfonate addina-K.
5. The negative electrode additive composition for lead-acid batteries according to claim 1, wherein said carbon black is selected from carbon black R425P.
6. A method of preparing a negative electrode additive composition for a lead-acid battery according to any of claims 1 to 6, comprising the steps of:
(1) mixing sodium lignosulphonate, humic acid, carbon black and barium sulfate to obtain a mixture;
(2) and performing ball milling on the mixture to obtain the negative electrode additive composition for the lead-acid battery.
7. The method according to claim 7, wherein the mixing in step (1) is carried out in a mixer; and (3) performing ball milling in a ball mill in the step (2).
8. According toThe method according to claim 8, wherein the grinding media in the ball mill has a density of 2.7-9 g/cm3The metal balls and/or metal oxide ceramic balls of (a); the volume filling rate of the grinding medium in the ball mill is 20-60%.
9. The preparation method according to claim 8, wherein the grinding media in the ball mill are graded by selecting metal balls and/or metal oxide ceramic balls with three sizes; respectively are metal balls or metal oxide ceramic balls with the diameter of 2-15 mm; metal balls or metal oxide ceramic balls with the diameter of 15-50 mm; metal balls or metal oxide ceramic balls with a diameter of 50-100 mm.
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| CN1747205A (en) * | 2005-10-14 | 2006-03-15 | 风帆股份有限公司 | Negative lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof |
| CN101161347A (en) * | 2006-10-13 | 2008-04-16 | 南京理工大学 | Bidirectional tosh grinding ultra-fine crashing objects and its method |
| CN101330140A (en) * | 2008-08-04 | 2008-12-24 | 风帆股份有限公司 | High-temperature lead-acid accumulator cathode diachylon and preparation method |
| CN101937996A (en) * | 2010-08-26 | 2011-01-05 | 风帆股份有限公司 | Colloid lead-acid storage battery cathode lead plaster for electric power assisted vehicle and preparation method |
| CN102299337A (en) * | 2011-07-26 | 2011-12-28 | 山东金科力电源科技有限公司 | Composite additive to negative electrodes for lead acid batteries, preparation method and application method thereof |
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2020
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1747205A (en) * | 2005-10-14 | 2006-03-15 | 风帆股份有限公司 | Negative lead cream of valve-controlled sealed plumbous acid accumulator for starting vehicle and production thereof |
| CN101161347A (en) * | 2006-10-13 | 2008-04-16 | 南京理工大学 | Bidirectional tosh grinding ultra-fine crashing objects and its method |
| CN101330140A (en) * | 2008-08-04 | 2008-12-24 | 风帆股份有限公司 | High-temperature lead-acid accumulator cathode diachylon and preparation method |
| CN101937996A (en) * | 2010-08-26 | 2011-01-05 | 风帆股份有限公司 | Colloid lead-acid storage battery cathode lead plaster for electric power assisted vehicle and preparation method |
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Application publication date: 20200710 |