Separator including coating layer including organic-inorganic hybrid composite compound battery including the same, and method of preparing the same
This application provides a separator, an electrical apparatus containing such separator, and preparation methods thereof. The separator includes a coating layer containing an organic-inorganic hybrid composite compound and provides improved performance in a number of aspects, and the organic-inorganic hybrid composite compound is formed by periodically assembling, along at least one spatial direction, basic units expressed by formula I, L x (M a C b ) y ·A z . This application further provides a battery and electrical device containing such separator, preparation methods thereof, organic-inorganic hybrid composite compound for improving performance of a separator.
1. A separator, comprising:
a polymer matrix layer; and
a coating layer applied on at least one surface of the polymer matrix layer, wherein the coating layer comprises an organic-inorganic hybrid composite compound, and the organic-inorganic hybrid composite compound is formed by periodically assembling, along at least one spatial direction, basic units expressed by formula I; wherein
L x (M a C b ) y ·A z formula I
in formula I, M is a cation of one or more metals selected from the following: 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, lanthanide metals, and actinide metals, wherein a is a value ranging from 0.1 to 10;
C is selected from one or more of the following atoms, atomic groups, small molecules, or anions: O, ═O, O 2 − , S 2− , Cl − , Br − , I − , CO, —OH, OH − , and H 2 O, wherein b is a value with a lower limit greater than 0 and an upper limit of 20;
y is a value ranging from 1 to 50;
when M is cations of two or more metals, a product of a and y represents the number of all metal cations in a single basic unit expressed by formula I;
L is selected from one or more of the following ligands: cyano group, CN—, thiocyano group, SCN—, nitrile, and salts, acids, esters, and anhydrides of the foregoing ligands, wherein the nitrile is one or more of the following: linear or branched C 2 -C 12 alkane dinitrile, linear or branched C 3 -C 12 alkane trinitrile, linear or branched C 4 -C 12 alkane tetranitrile, linear or branched chain C 2 -C 12 alkene dinitrile, linear or branched C 3 -C 12 alkene trinitrile, linear or branched C 4 -C 12 alkene tetranitrile, linear or branched C 2 -C 12 alkyne dinitrile, linear or branched C 3 -C 12 alkyne trinitriles, and linear or branched C 4 -C 12 alkyne tetranitriles, wherein one or more hydrogen atoms in the nitrile are optionally substituted by one or more substituent groups selected from the following groups: cyano group, nitro group, amino group, aldehyde group, carboxyl group, halogen, C 1 -C 8 alkyl group, C 1 -C 8 hydroxyalkyl group, C 1 -C 8 alkoxy group, C 2 -C 8 alkenyl group, C 2 -C 8 alkynyl group, C 3 -C 16 cycloalkyl group, C 6 -C 20 aryl group, C 6 -C 20 heteroaryl group, or any combination thereof, wherein x is a value ranging from 1 to 50; and
A is an atom or cation selected from one or more of the following metal elements: Li, Na, K, Rb, Cs, Be, Sr, Zn, Al, Mg, and Ca; or is selected from one or more of the following molecules: H 2 , O 2 , H 2 O, CO 2 , NH 3 , CH 4 , methyl formate, ethyl acetate, and propylene carbonate, wherein z is a value ranging from 0 to 100,
wherein C is connected to M to form a cluster structure, and the cluster structure and L serve as constituent parts of the basic units so as to form the organic-inorganic hybrid composite compound through periodical self-assembly.
2. The separator according to claim 1 , wherein M is a cation of one or more metals selected from the following: Co, Fe, Mn, and Ni; and
L is cyano group or CN—.
3. The separator according to claim 1 , wherein the basic unit is selected from one or more of the following: (CN) 6 [FeMn]·K 2 (H 2 O) 0.15 , (CN) 6 [FeMn]·K 2 (CO 2 ) 0.1 , and (CN) 3.42 [Fe 0.55 Mn]·Na 0.27 (H 2 O) 1.5 .
4. The separator according to claim 1 , wherein the coating layer further comprises one or more components selected from the following: binder, inorganic particles, stabilizer, wetting agent, rheology modifier, defoamer, thickener, pH adjuster, and preservative; and/or
the coating layer further comprises inorganic particles, and the inorganic particle is selected from at least one of the following: boehmite, molecular sieve, zeolite, alumina, alumina hydroxide, silica, aluminum nitride, silicon carbide, MgO, CaO, ZnO, ZrO 2 , TiO 2 , and a mixture thereof; and/or
a weight ratio of the organic-inorganic hybrid composite compound to the inorganic particles is 1:5 to 5:1.
5. The separator according to claim 1 , wherein 0.5≤x:y≤6; and/or
0.5≤a:b≤8.
6. The separator according to claim 5 , wherein M is a cation of one or more metals selected from the following: Co, Fe, Mn, and Ni; and
L is cyano group or CN—.
7. The separator according to claim 5 , wherein the basic unit is selected from one or more of the following: (CN) 6 [FeMn]·K 2 (H 2 O) 0.15 , (CN) 6 [FeMn]·K 2 (CO 2 ) 0.1 , and (CN) 3.42 [Fe 0.55 Mn]· Na 0.27 (H 2 O) 1.5 .
8. The separator according to claim 5 , wherein the metal cation M, ligand L, and C form a cubic or quasi-cubic basic unit structure, wherein M or a combination of M and C is located at a vertex of the basic unit, and the ligand L is located on an edge of the basic unit, the basic unit has pores, when z is not zero, A is located in the pores of the basic unit, and the basic unit is periodically assembled along at least one spatial direction to form the organic-inorganic hybrid composite compound.
9. The separator according to claim 5 , wherein the coating layer further comprises one or more components selected from the following: binder, inorganic particles, stabilizer, wetting agent, rheology modifier, defoamer, thickener, pH adjuster, and preservative; and/or
the coating layer further comprises inorganic particles, and the inorganic particle is selected from at least one of the following: boehmite, molecular sieve, zeolite, alumina, alumina hydroxide, silica, aluminum nitride, silicon carbide, MgO, CaO, ZnO, ZrO 2 , TiO 2 , and a mixture thereof; and/or
a weight ratio of the organic-inorganic hybrid composite compound to the inorganic particles is 1:5 to 5:1.
10. The separator according to claim 1 , wherein in the organic-inorganic hybrid composite compound, the number of basic units expressed by formula I that are periodically assembled along at least one spatial direction is an integer ranging from 3 to 10,000.
11. The separator according to claim 10 , wherein 0.5≤x:y≤6; and/or
0.5≤a:b≤8.
12. The separator according to claim 10 , wherein M is a cation of one or more metals selected from the following: Co, Fe, Mn, and Ni; and
L is cyano group or CN—.
13. The separator according to claim 10 , wherein the basic unit is selected from one or more of the following: (CN) 6 [FeMn]·K 2 (H 2 O) 0.15 , (CN) 6 [FeMn]·K 2 (CO 2 ) 0.1 , and (CN) 3.42 [Fe 0.55 Mn]·Na 0.27 (H 2 O) 1.5 .
14. The separator according to claim 10 , wherein the metal cation M, ligand L, and C form a cubic or quasi-cubic basic unit structure, wherein M or a combination of M and C is located at a vertex of the basic unit, and the ligand L is located on an edge of the basic unit, the basic unit has pores, when z is not zero, A is located in the pores of the basic unit, and the basic unit is periodically assembled along at least one spatial direction to form the organic-inorganic hybrid composite compound.
15. The separator according to claim 10 , wherein the coating layer further comprises one or more components selected from the following: binder, inorganic particles, stabilizer, wetting agent, rheology modifier, defoamer, thickener, pH adjuster, and preservative; and/or
the coating layer further comprises inorganic particles, and the inorganic particle is selected from at least one of the following: boehmite, molecular sieve, zeolite, alumina, alumina hydroxide, silica, aluminum nitride, silicon carbide, MgO, CaO, ZnO, ZrO 2 , TiO 2 , and a mixture thereof; and/or
a weight ratio of the organic-inorganic hybrid composite compound to the inorganic particles is 1:5 to 5:1.
16. The separator according to claim 1 , wherein the metal cation M, ligand L, and C form a cubic or quasi-cubic basic unit structure, wherein M or a combination of M and C is located at a vertex of the basic unit, and the ligand L is located on an edge of the basic unit, the basic unit has pores, when z is not zero, A is located in the pores of the basic unit, and the basic unit is periodically assembled along at least one spatial direction to form the organic-inorganic hybrid composite compound.
17. The separator according to claim 16 , wherein M is a cation of one or more metals selected from the following: Co, Fe, Mn, and Ni; and
L is cyano group or CN—.
18. The separator according to claim 16 , wherein the basic unit is selected from one or more of the following: (CN) 6 [FeMn]·K 2 (H 2 O) 0.15 , (CN)·[FeMn]·K 2 (CO 2 ) 0.1 , and (CN) 3.42 [Fe 0.55 Mn]·Na 0.27 (H 2 O) 1.5 .
19. A battery, comprising the separator according to claim 1 .
20. A preparation method of the separator according to claim 1 , wherein the method comprises:
providing the polymer matrix layer; and
forming, on at least one surface of the polymer matrix layer, the coating layer comprising the organic-inorganic hybrid composite compound.