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US-12620674-B2 - Separator, and secondary battery, battery module, battery pack, and apparatus including the same

US12620674B2US 12620674 B2US12620674 B2US 12620674B2US-12620674-B2

Abstract

The present application provides a separator, which may include a substrate and a coating provided on at least one surface of the substrate, the coating including inorganic particles, first and second organic particles, organic-inorganic hybrid composite compound particles, and a first binder; where the first organic particles and the second organic particles may be embedded in the inorganic particles and the organic-inorganic hybrid composite compound particles and form bulges on a surface of the coating; the first organic particles and the second organic particles each may be independently one or more polymers containing one or more groups selected from: halogen, a phenyl group, an epoxy group, a cyano group, an ester group, an amide group, a hydroxyl group, a carboxyl group, a sulfonyl ester group, and a pyrrolidone group; and the first binder may include one or more linear copolymers containing a hydroxyl group and a carboxylate moiety.

Inventors

  • Haiyi HONG
  • Jianrui YANG

Assignees

  • CONTEMPORARY AMPEREX TECHNOLOGY (HONG KONG) LIMITED

Dates

Publication Date
20260505
Application Date
20231106

Claims (18)

  1. 1 . A separator, comprising: a substrate, and a coating provided on at least one surface of the substrate, the coating comprising inorganic particles, first organic particles, second organic particles, organic-inorganic hybrid composite compound particles, and a first binder; wherein: the first organic particles and the second organic particles are embedded between the inorganic particles and the organic-inorganic hybrid composite compound particles and form bulges on a surface of the coating; the first organic particles and the second organic particles each are independently one or more polymers containing one or more groups selected from: halogen, a phenyl group, an epoxy group, a cyano group, an ester group, an amide group, a hydroxyl group, a carboxyl group, a sulfonyl ester group, and a pyrrolidone group; the first binder comprises one or more linear copolymers containing a hydroxyl group and a carboxylate moiety; the organic-inorganic hybrid composite compound contains metal atoms and/or metal cations, and organic ligands, and basic units constituting the organic-inorganic hybrid composite compound are periodically assembled in at least one spatial direction; Dv50 of the first organic particles is in a range of 5 μm to 30 μm, Dv50 of the second organic particles is in a range of 2 μm to 11.5 μm, and the Dv50 of the first organic particles is larger than the Dv50 of the second organic particles; the first organic particles are all secondary particles and the second organic particles are all primary particles; and the organic-inorganic hybrid composite compound is (CN) 6 [FeMn]K 2 , (CN) 5.7 [Co 0.95 Fe]K 1.8 , or (CN) 5.98 [Fe 0.99 Mn]Na 1.99 .
  2. 2 . The separator according to claim 1 , wherein number-average particle sizes of the inorganic particles, the first organic particles, the second organic particles and the organic-inorganic hybrid composite compound particles are respectively defined as R I , R O1 , R O2 and R O-I , which satisfy 0.2 μm ≤ min ⁢ { R O ⁢ 1 , R O ⁢ 2 } - max ⁢ { R I , R O - I } ≤ 10 ⁢ μm .
  3. 3 . The separator according to claim 1 , wherein Dv50 of the first organic particles is 8 μm to 18 μm; and/or Dv50 of the second organic particles is 3 μm to 11.5 μm; and/or Dv50 of the organic-inorganic hybrid composite compound particles is 0.01 μm to 3 μm.
  4. 4 . The separator according to claim 1 , wherein the first organic particles are particles of a homopolymer or copolymer containing one or more substituent groups selected from halogen, a phenyl group, an epoxy group, a cyano group, an ester group, and an amide group; and/or the second organic particles are particles of a homopolymer or copolymer containing one or more substituent groups selected from a phenyl group, an epoxy group, a cyano group, an ester group, a hydroxyl group, a carboxyl group, a sulfonyl ester group, and a pyrrolidone group.
  5. 5 . The separator according to claim 1 , wherein a specific surface area of the organic-inorganic hybrid composite compound particles is 1 m 2 /g to 50 m 2 /g.
  6. 6 . The separator according to claim 1 , wherein the one or more linear copolymers is a polymerization product containing the following types of monomer: (1) a first type of monomer, the first type of monomer is selected from at least one of: acrylic acid, methacrylic acid, methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, methylolacrylamide, acrylamide, styrene, and acrylonitrile; (2) a second type of monomer, the second type of monomer is selected from at least one of: ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, cyclohexyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, n-hexyl methacrylate, tridecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethyleneurea ethyl methacrylate, dicyclopentene ethoxy methacrylate, tetrahydrofuryl methacrylate, trifluoroethyl methacrylate, ethyleneurea ethyl methacrylate, propylene methacrylate, dicyclopentene ethoxy methacrylate, tetrahydrofuryl methacrylate, and trifluoroethyl methacrylate; (3) a third type of monomer, the third type of monomer is selected from at least one of: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane, N-methylolacrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide (DAAM), acetoacetoxy ethyl methacrylate (AAEM), divinylbenzene, and epoxy resin with an epoxy value of 0.35˜0.50; and (4) a fourth type of monomer, the fourth type of monomer is selected from at least one of: polyvinyl alcohol, polypropylene alcohol, polypropylene glycol, polyethylene glycol, and polyvinyl acid alcohol.
  7. 7 . The separator according to claim 6 , wherein after polymerizing the first type of monomer, the second type of monomer, the third type of monomer and the fourth type of monomer, a pH regulator is added to adjust pH to 5-7, and the pH regulator is selected from at least one of: lithium hydroxide, calcium hydroxide, sodium hydroxide and ammonia water.
  8. 8 . The separator according to claim 6 , wherein the first type of monomer accounts for 60 wt % to 85 wt %; and/or the second type of monomer accounts for 1 wt % to 10 wt %; and/or the third type of monomer accounts for 1 wt % to 10 wt %; and/or the fourth type of monomer accounts for 1 wt % to 20 wt %, calculated based on a total weight of all monomers contained in the one or more linear copolymers.
  9. 9 . The separator according to claim 1 , wherein the one or more linear copolymers is a polymer selected from: A. a 30% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-10% n-butyl acrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer having a Tg of 160° C.; B. a 30% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-10% n-butyl acrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer having a Tg of 140° C.; C. a 30% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-10% n-butyl acrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer having a Tg of 150° C.; D. a 35% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-5% n-butyl acrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer; E. a 30% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-10% n-butyl acrylate-3% 2-hydroxyethyl methacrylate-12% polyvinyl alcohol copolymer; F. a 30% styrene-15% methacrylic acid-15% acrylamide-15% acrylic acid-5% acrylonitrile-5% n-butyl acrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer; G. a 40% styrene-15% acrylamide-15% acrylic acid-10% n-butyl acrylate-5% n-hexyl methacrylate-2% 2-hydroxyethyl methacrylate-1% E44 epoxy resin-12% polyvinyl alcohol copolymer; and H. a 35% styrene-15% methacrylic acid-10% acrylamide-15% acrylic acid-5% acrylonitrile-5% n-butyl acrylate-2% divinylbenzene-1% E44 epoxy resin-12% polyvinyl alcohol copolymer; wherein an average epoxy value of the E44 epoxy resin is 0.44, an alcoholysis degree of the polyvinyl alcohol is 88% and a degree of polymerization of the polyvinyl alcohol is 1000, and the percentage is a weight percentage of a monomer, calculated based on a total weight of all monomers.
  10. 10 . The separator according to claim 1 , wherein a weight-average molecular weight of the one or more linear copolymers is 1×10 3 g/mol to 200×10 3 g/mol.
  11. 11 . The separator according to claim 1 , wherein the first organic particles are at least one selected from: a homopolymer or copolymer of fluorine-containing alkenyl monomer units, a homopolymer or copolymer of olefin monomer units, a homopolymer or copolymer of unsaturated nitrile monomer units, a homopolymer or copolymer of alkylene oxide monomer units, a bipolymer, homopolymer or copolymer of monosaccharide monomer units, and modified compounds of the above homopolymers or copolymers.
  12. 12 . The separator according to claim 1 , wherein the second organic particles are at least one selected from: a homopolymer or copolymer of acrylate monomer units, a homopolymer or copolymer of acrylic acid monomer units, a homopolymer or copolymer of unsaturated nitrile monomer units, a homopolymer or copolymer of ethylenic monomer units, a homopolymer or copolymer of styrene monomer units, a homopolymer or copolymer of epoxy monomer units, a polyurethane compound, a rubber compound, a bipolymer, homopolymer or copolymer of monosaccharide monomer units, and modified compounds of the above homopolymers or copolymers.
  13. 13 . The separator according to claim 1 , wherein, calculated based on a total weight of the coating, a content of the inorganic particles is 10 wt % to 44 wt %; and/or a content of the organic-inorganic hybrid composite compound particles is 30 wt % to 74 wt %; and/or a content of the first binder is 2 wt % to 8 wt %; and/or a total content of the first organic particles and the second organic particles is 16 wt % to 31 wt %.
  14. 14 . The separator according to claim 1 , wherein a weight ratio of the first organic particles to the second organic particles is 1:2 to 6:1.
  15. 15 . The separator according to claim 1 , wherein viscosity of the first binder is 150 mPa·s-400 mPa·s.
  16. 16 . The separator according to claim 1 , wherein a ratio of a total weight of the first organic particles and the second organic particles to a total weight of the inorganic particles and the organic-inorganic hybrid composite compound particles is 1:5 to 1:2.
  17. 17 . A secondary battery, comprising the separator according to claim 1 .
  18. 18 . A power consumption apparatus, comprising the secondary battery according to claim 17 .

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application is a continuation of International Application No. PCT/CN2021/143124, filed on Dec. 30, 2021, which is incorporated herein by reference in its entirety. TECHNICAL FIELD The present application relates to the field of lithium battery technologies, and in particular, to a separator, a preparation method thereof, and a secondary battery, battery module, battery pack, and apparatus including the same. BACKGROUND Lithium-ion secondary batteries are widely applied to a variety of electronic products and vehicles due to their various advantages, and accompany people day and night. Therefore, the safety issue of the lithium-ion secondary batteries has become one of the most important topics in the industry. A separator is an important part to ensure the safety of a battery. If the separator is damaged (such as high temperature shrinkage, melting, oxidation and/or breakage), it may cause a short circuit in an interior of the battery, resulting in a safety incident. In order to improve the safety of a lithium-ion battery, many technical solutions have been proposed in the prior art. However, so far, there is no solution that could take into account performance in various aspects of a battery while improving safety. Therefore, at present, how to obtain a secondary battery having good safety performance and taking into account other performance is still a challenge in this field. SUMMARY The present application is made in view of the foregoing problem, the objective is to provide a separator with good safety performance, low impedance, and good infiltration performance of an electrolytic solution, which could improve cycle performance and safety of a battery. In order to achieve the foregoing objective, the present application provides a separator, and a secondary battery, battery module, battery pack, and apparatus including the separator. In a first aspect of the present application, a separator is provided, including: a substrate, and a coating provided on at least one surface of the substrate, the coating including inorganic particles, first organic particles, second organic particles, organic-inorganic hybrid composite compound particles, and a first binder; where:the first organic particles and the second organic particles are embedded between the inorganic particles and the organic-inorganic hybrid composite compound particles and form bulges on a surface of the coating;the first organic particles and the second organic particles each are independently one or more polymers containing one or more groups selected from: halogen, a phenyl group, an epoxy group, a cyano group, an ester group, an amide group, a hydroxyl group, a carboxyl group, a sulfonyl ester group, and a pyrrolidone group;the first binder includes one or more linear copolymers containing a hydroxyl group and a carboxylate moiety; optionally, the first binder includes one or more linear copolymers containing a hydroxyl group, a carboxylate moiety, an amide group, and an epoxy group; optionally, the carboxylate moiety is a lithium carboxylate moiety; andthe organic-inorganic hybrid composite compound contains metal atoms and/or metal cations, and organic ligands, and basic units constituting the organic-inorganic hybrid composite compound are periodically assembled in at least one spatial direction. In any embodiment, in the separator of the present application, the organic-inorganic hybrid composite compound is constituted by periodically assembling basic units shown in formula I in at least one spatial direction: in formula I,M is a cation of one or more metals selected from: Zn, Co, Cu, Fe, Cd, Mn, Ag, Rh, Ru, Be, Mg, Al, Sc, Cr, Ni, Y, Ti, Zr, Hf, Li, Na, K, In, Ca, Sr, Pb, a lanthanide series metal, and an actinide series metal, and y is a value in a range of 0.1 to 10; optionally, M is a cation of one or more metals selected from: Zn, Co, Cu, Fe, Cd, Mn, Mg, Cr, Ni, Y, Na, and K; more optionally, M is a cation of one or more metals selected from Co, Fe, Mn and Ni;when M is a cation of two or more metals, y represents the number of all metal cations in a basic unit M shown in a single formula I;A is an atom or a cation of one or more metal elements selected from: Li, Na, K, Rb, Cs, Be, Sr, Zn, Al, Mg and Ca, and/or one or more molecules selected from: Hz, O2, H2O, CO2, NH3, CH4, methyl formate, ethyl acetate, and propylene carbonate, and z is a value from 0 to 100, optionally, a value from 1.8 to 2; optionally, A is an atom or a cation of one or more metal elements and/or one or more molecules selected from: Li, Na, K, Zn, H2O, CO2, NH3, CH4, and methyl formate; more optionally, A is an atom or cation of one or more metal elements selected from: Li, Na and K; andL is one or more ligands selected from: a cyano group, CN−, a thiocyanate group, SCN−, nitrile and its salts, acid radical, ester and anhydride; optionally, L is one or more ligands selected from: a cyano group, a thiocyanate