US 12,444,807 B2
Modified polyphenylene sulfide (PPS) and PPS modification method, PPS solid separator, prefabricated zinc salt separator and manufacturing method thereof, to-be-filled zinc-manganese secondary battery, and manufacturing and application methods thereof
Haitao Zhou, Zhenjiang (CN); Hongquan Gao, Zhenjiang (CN); Jianchun Wu, Zhenjiang (CN); Haiyun Zhou, Zhenjiang (CN); Shengjie Yao, Zhenjiang (CN); Hongwen Zhu, Zhenjiang (CN); and Rongfei Yan, Zhenjiang (CN)
Assigned to JIANGSU UNIVERSITY, Zhenjiang (CN)
Appl. No. 18/860,698
Filed by JIANGSU UNIVERSITY, Zhenjiang (CN)
PCT Filed Apr. 8, 2024, PCT No. PCT/CN2024/086497
§ 371(c)(1), (2) Date Oct. 28, 2024,
PCT Pub. No. WO2024/212909, PCT Pub. Date Oct. 17, 2024.
Claims priority of application No. 202310393324.5 (CN), filed on Apr. 13, 2023; and application No. 202410046169.4 (CN), filed on Jan. 12, 2024.
Prior Publication US 2025/0174824 A1, May 29, 2025
Int. Cl. H01M 50/489 (2021.01); C08J 3/20 (2006.01); C08K 5/136 (2006.01); H01M 4/04 (2006.01); H01M 4/24 (2006.01); H01M 4/26 (2006.01); H01M 4/38 (2006.01); H01M 4/62 (2006.01); H01M 4/66 (2006.01); H01M 10/04 (2006.01); H01M 10/26 (2006.01); H01M 10/28 (2006.01); H01M 50/105 (2021.01); H01M 50/121 (2021.01); H01M 50/124 (2021.01); H01M 50/131 (2021.01); H01M 50/403 (2021.01); H01M 50/414 (2021.01); H01M 50/457 (2021.01); H01M 50/538 (2021.01); H01M 50/595 (2021.01)
CPC H01M 50/414 (2021.01) [C08J 3/203 (2013.01); C08K 5/136 (2013.01); H01M 4/043 (2013.01); H01M 4/24 (2013.01); H01M 4/26 (2013.01); H01M 4/38 (2013.01); H01M 4/623 (2013.01); H01M 4/625 (2013.01); H01M 4/662 (2013.01); H01M 10/0431 (2013.01); H01M 10/049 (2013.01); H01M 10/26 (2013.01); H01M 10/288 (2013.01); H01M 50/105 (2021.01); H01M 50/121 (2021.01); H01M 50/124 (2021.01); H01M 50/131 (2021.01); H01M 50/403 (2021.01); H01M 50/457 (2021.01); H01M 50/489 (2021.01); H01M 50/538 (2021.01); H01M 50/595 (2021.01); C08J 2381/02 (2013.01); H01M 2300/0011 (2013.01)] 12 Claims
OG exemplary drawing
 
1. A manufacturing method of a to-be-filled zinc-manganese secondary battery, wherein the to-be-filled zinc-manganese secondary battery is manufactured with a prefabricated zinc salt separator, wherein a manufacturing method of the prefabricated zinc salt separator, comprises:
(1) providing one of a polyphenylene sulfide (PPS) solid separator (A) and an upper support separator (B) with a glue liquid (C) by dipping or coating, and bonding the PPS solid separator (A) and the upper support separator (B) together with the glue liquid (C) being located between the PPS solid separator (A) and the upper support separator (B); laminating the upper support separator (B) with the PPS solid separator (A) through roll-pressing; and drying the upper support separator (B) and the PPS solid separator (A) that are laminated, to obtain a double-layer prefabricated zinc salt separator (D); and
(2) providing one of an exposed surface of the PPS solid separator (A) of the double-layer prefabricated zinc salt separator (D) and a lower support separator (F) with a glue liquid (E) by dipping or coating, and bonding the exposed surface of the PPS solid separator (A) of the double-layer prefabricated zinc salt separator (D) and the lower support separator (F) together with the glue liquid (E) being located between the exposed surface of the PPS solid separator (A) of the double-layer prefabricated zinc salt separator (D) and the lower support separator (F); laminating the lower support separator (F) with the double-layer prefabricated zinc salt separator (D) to obtain a three-layer separator; and drying the three-layer separator to obtain a prefabricated zinc salt separator (H),
wherein the upper support separator (B) and the lower support separator (F) are both porous separators, and the glue liquid (C) and the glue liquid (E) are each a mixture of an organic adhesive and/or an inorganic adhesive, an electrolyte zinc salt, and a solvent,
wherein the prefabricated zinc salt separator comprises the PPS solid separator (A), and the upper support separator (B) and the lower support separator (F) located on both sides of the PPS solid separator (A), wherein a mixture comprising the organic adhesive and/or the inorganic adhesive and the electrolyte zinc salt is filled between the upper support separator (B) and the PPS solid separator (A) and between the lower support separator (F) and the PPS solid separator (A),
wherein the prefabricated zinc salt separator (H) is arranged between a manganese oxide positive electrode and a zinc negative electrode, electrode tabs are welded, a battery cell is prepared by a stacking machine or a winding machine, the battery cell is placed into a battery case or an aluminum-plastic film pouch, and the battery case or the aluminum-plastic film pouch is sealed and stored for later use, wherein the battery case or the aluminum-plastic film pouch is provided with a sealable liquid injection port,
wherein a manufacturing method of the manganese oxide positive electrode comprises: mixing manganese dioxide with polytetrafluoroethylene (PTFE) first;
using a dry supersonic jet gas to allow molecular chains of the PTFE to open and physically adhere to a positive electrode material powder below a glass transition temperature of the PTFE;
spraying an alcohol solution onto fiberized powder;
performing internal mixing and shearing granulation followed by hot-rolling to form a positive electrode film;
laminating multiple layers of the positive electrode film through multiple cold rolling to form a composite positive electrode self-supporting film with a thickness of 100 μm to 150 μm;
and laminating the composite positive electrode self-supporting film with a glue-coated sandblasted stainless steel foil through a hot roller press.