CN116868397A - Positive electrode - Google Patents
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- CN116868397A CN116868397A CN202180086812.0A CN202180086812A CN116868397A CN 116868397 A CN116868397 A CN 116868397A CN 202180086812 A CN202180086812 A CN 202180086812A CN 116868397 A CN116868397 A CN 116868397A
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- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 72
- 239000007774 positive electrode material Substances 0.000 claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 95
- -1 oxypropylene units Chemical group 0.000 claims description 65
- 125000000217 alkyl group Chemical group 0.000 claims description 64
- 229920001296 polysiloxane Polymers 0.000 claims description 52
- 239000000178 monomer Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 39
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 37
- 150000004820 halides Chemical class 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000623 heterocyclic group Chemical group 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 125000006353 oxyethylene group Chemical group 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 239000000843 powder Substances 0.000 description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 21
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- 238000009616 inductively coupled plasma Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- 229940021013 electrolyte solution Drugs 0.000 description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 101150088727 CEX1 gene Proteins 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000096 monohydride Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 239000002253 acid Chemical group 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010296 bead milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
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- 239000008151 electrolyte solution Substances 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 101100439208 Caenorhabditis elegans cex-1 gene Proteins 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
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- VMWNQDUVQKEIOC-CYBMUJFWSA-N apomorphine Chemical group C([C@H]1N(C)CC2)C3=CC=C(O)C(O)=C3C3=C1C2=CC=C3 VMWNQDUVQKEIOC-CYBMUJFWSA-N 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention provides a positive electrode for a lithium ion secondary battery comprising a positive electrode active material and at least one polymer electrolyte that is a polyether polymer, the positive electrode active material comprising at least an element selected from the group consisting of Li, M 'and oxygen, wherein the metal M' has the formula: ni (Ni) 1‑x‑y‑z Mn x Co y A z Wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40, and 0.00.ltoreq.z.ltoreq.0.10, wherein when A is present, A is different from Ni, mn, co, and Li, and preferably is at least one of B, mg, al, nb, ti, Y, W, S, ba, sr and Zr.
Description
Technical Field
The present invention relates to a positive electrode for a lithium ion secondary battery, the positive electrode comprising a positive electrode active material and at least one polymer electrolyte.
Background
Polymer electrolytes are an interesting alternative to liquid electrolytes in batteries. Against this background, polyethylene oxide (PEO) based electrolytes have been widely studied in the literature.
For example, ruoyuan Tao et al in j.appl. Electrochem.35, 163-168 (2005) disclose a positive electrode comprising poly (ethylene oxide) and lithium bis (trifluoromethylsulfonyl) imide (Li (N (SO) 2 CF 3 ) 2 ) Also known as LiTFSI. PEO and LiTFSI were dissolved in acetonitrile to prepare electrolyte solutions. The positive electrode active material is added to the electrolyte solution.
U.S. Pat. No. 7,585,934 B2 discloses the use of EO/PO/AGE and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, li (N (SO 2CF 3) 2) as solid polymer electrolyte membranes this document discloses in the working examples the copolymerization procedure of EO, PO and AGE in particular LiTFSI is added as a Li salt to a polyether polymer composition comprising the EO/PO/AGE copolymer in such an amount that the ratio of (moles of lithium atoms in the electrolyte salt)/(moles of oxygen atoms in the polyether polymer) is 0.05.
Despite recent advances in this area, capacity leakage remains a problem for positive electrodes comprising PEO-based solid electrolytes. Capacity leakage is a phenomenon according to which an electrolyte acquires electron conductivity, resulting in leakage of electron current from an anode to a cathode.
There is therefore a need for improved positive electrodes, particularly positive electrodes with reduced capacity leakage when used in batteries.
Disclosure of Invention
The inventors have surprisingly found that an improved positive electrode meeting the above-mentioned needs can be provided.
Accordingly, the main object of the present invention is a positive electrode for a lithium ion secondary battery comprising a positive electrode active material and at least one polymer electrolyte, the positive electrode active material comprising at least Li, M 'and oxygen elements, wherein M' consists of Ni, mn, co and a, the positive electrode material having a (1-x-y-z): (x+y+z) Ni (mn+co+a) molar ratio (or atomic ratio), wherein 0.00 +.ltoreq.x.ltoreq.0.70, 0.00 +.y.ltoreq.0.40 and 0.00 +.ltoreq.z.ltoreq.0.10, measured by ICP, wherein when a is present, a is different from Ni, mn, co and Li, and preferably at least one of Al or: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
a) At least 70.0 mole% of oxyethylene units (EO);
b) 0.0 to 10.0 mole% oxypropylene units (PO); and
c) 1.00 to 4.0 mol% of recurring units derived from at least one monomer of the general formula (I) or (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-each of R1 and R2 is the same OR different from each other and is at each occurrence a C1-6 alkanediyl group, wherein said C1-6 alkanediyl group is optionally substituted with one OR more substituents selected from the group consisting of halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, OR8, and wherein each R8 is the same OR different from each other and is at each occurrence independently selected from the group consisting of hydrogen and C1-4 alkyl; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
Each of R3, R4, R5, R6 and R7 is the same OR different from each other and is independently selected at each occurrence from C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, heterocyclyl, wherein the C1-6 alkyl, C3-6 cycloalkyl, aryl, C1-6 alkoxy, heterocyclyl is optionally substituted with one OR more substituents selected from the group consisting of halide, C1-4 alkyl, C3-6 cycloalkyl, CF3, OR9, and wherein each R9 is the same OR different from each other and is independently selected at each occurrence from the group consisting of hydrogen, C1-4 alkyl and hydroxy protecting group,
-m is an integer of at least 3; and is also provided with
Wherein the at least one polysiloxane compound having formula (III) is grafted onto the at least one polymer (P) by reaction of at least a portion of the-ch=ch2 moiety of monomer (M) with the H-Si moiety of the polysiloxane compound having formula (III).
A second object of the present invention relates to a positive electrode for a lithium ion secondary battery, comprising a positive electrode active material and at least one polymer electrolyte, said positive electrode active material comprising at least an element selected from the group consisting of Li, M 'and oxygen, wherein the metal M' has the formula: ni (Ni) 1-x-y-z Mn x Co y A z Wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40, and 0.00.ltoreq.z.ltoreq.0.10, as measured by ICP, wherein when A is present, A is different from Ni, mn, co and Li, and is preferably at least one of: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. at least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
a) At least 70.0 mole% of oxyethylene units (EO);
b) 0.0 to 10.0 mole% oxypropylene units (PO); and
c) 1.00 to 4.0 mol% of recurring units derived from at least one monomer of the general formula (I) or (II) [ monomer (M) hereinafter) ]:
Wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
It is another object of the present invention to provide a polymer battery including the positive electrode.
It is another object of the present invention to provide an electrochemical cell comprising the positive electrode.
It is another object of the invention to provide the use of the positive electrode in a battery.
Detailed Description
Positive electrode
As used herein and in the claims, the term "comprising" should not be construed as limited to the manner set forth hereinafter; it does not exclude other elements or steps. It is to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components or groups thereof. Thus, the scope of the expression "composition comprising component a and component B" should not be limited to compositions consisting of only component a and component B. This means that the only relevant components of the composition are a and B with respect to the present invention. Thus, the terms "comprising" and "including" encompass the more limiting terms "consisting essentially of …" and "consisting of …".
As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
The term "positive electrode active material" is intended to mean a material that is electrochemically active in the positive electrode. The active material is capable of capturing and releasing Li ions when subjected to a voltage change over a predetermined period of time.
The inventors have surprisingly found that when the positive electrode according to the invention is used in a battery, in particular in a solid state lithium ion battery, the capacity leakage is reduced, resulting in a battery with improved performance, as demonstrated in the working examples.
In the context of the present invention, the term "positive electrode active material" is defined as a material that is electrochemically active in the positive electrode. The active material is capable of capturing and releasing Li ions when subjected to a voltage change over a predetermined period of time.
In the context of the present invention, the expression "at least one polyether polymer [ polymer (P) hereinafter) ] is intended to mean one or more than one polymer (P). Similarly, the expressions "at least one polysiloxane compound of formula (III)" and "at least one polymer electrolyte" are intended to mean one or more than one polysiloxane compound of formula (III) and correspondingly one or more than one polymer electrolyte.
In the remainder of this document, for the purposes of the present invention, the expressions "polymer (P)", "polymer electrolyte" and "polysiloxane compound having formula (III)" should be understood as both plural and singular.
As used herein, the term "alkyl" has the broadest meaning generally understood in the art and may include moieties that are linear or branched, or a combination thereof.
The term "alkyl", alone or in combination, means a linear or branched alkane derived group, e.g., C F-G Alkyl defines a straight or branched alkyl group having F to G carbon atoms, e.g. C 1-4 Alkyl defines a straight-chain or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl (isopropyl), 1-butyl, 2-methyl-2-propyl (tert-butyl), 2-methyl-1-propyl (isobutyl).
The term "cycloalkyl", alone or in combination, means a cyclic alkane-derived group, e.g., C L-M Cycloalkyl defines a cyclic alkyl group having L to M carbon atoms, e.g. C 3-6 Cycloalkyl defines a cyclic alkyl group having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
The term "aryl", alone or in combination, means phenyl, naphthyl or anthracyl, optionally fused to a cycloalkyl or heterocyclyl carbocycle having preferably 5-7, more preferably 5-6 ring members and/or optionally substituted with 1 to 5 groups or substituents. The aryl group may be optionally substituted whereby the substituent is attached to the aryl group at one point or whereby the substituent is attached to the aryl group at two points to form a bicyclic ring system, e.g., benzodioxole, benzodioxane, benzimidazole.
The term "heterocyclyl", alone or in combination, means a cyclic alkane-derived group in which at least one carbon atom is replaced by a heteroatom independently selected from oxygen, nitrogen and sulfur, such as pyrrolidine, piperidine or morpholine and the like.
The term "alkoxy", alone or in combination, means a linear or branched alkane-derived group in which the carbon atom bearing the group is replaced with an oxygen atom. Alkoxy moieties having a range of from-0 to R x Structure, wherein R is x Is alkyl.
The term "alkanediyl", alone or in combination, means a divalent group derived from a straight or branched chain alkyl group.
The first aspect of the present invention provides a positive electrode for a lithium ion secondary battery, the positive electrode comprising a positive electrode active material and at least one polymer electrolyte, the positive electrode active material comprising Ni, mn, co and A, the positive electrode material having a (1-x-y-z): (x+y+z) Ni (Mn+Co+A) molar ratio as measured by ICP, wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40 and 0.00.ltoreq.z.ltoreq.0.10, wherein when A is present, A is different from Ni, mn, co and Li, and preferably is at least one of Al or: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
-at least 70.0 mole% of oxyethylene units (EO);
-0.0 to 10.0 mol% oxypropylene units (PO); and
-1.00 to 4.0 mol% of recurring units derived from at least one monomer of formula (I) or formula (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
Alternatively, one embodiment of the present invention provides a positive electrode for a lithium ion secondary battery, the positive electrode comprising a positive electrode active material and at least one polymer electrolyte, the positive electrode active material comprising at least Li, M 'and an oxygen element, wherein M' consists of Ni, mn, co and A, the positive electrode material having a (1-x-y-z): (x+y+z) Ni (Mn+Co+A) molar ratio as measured by ICP, wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40 and 0.00.ltoreq.z.ltoreq.0.10, wherein when A is present, A is different from Ni, mn, co and Li, and preferably at least one of Al or: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
-at least 70.0 mole% of oxyethylene units (EO);
-0.0 to 10.0 mol% oxypropylene units (PO); and
-1.00 to 4.0 mol% of recurring units derived from at least one monomer of formula (I) or formula (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted by one or more substituents andand wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
As described above, the polymer (P) comprises
a) At least 70.0 mole% of recurring units of ethylene oxide units (EO);
b) 0.0 to 10.0 mole% oxypropylene units (PO); and
c) 1.00 to 4.0 mol% of recurring units derived from at least one monomer of the general formula (I) or (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
each of X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutanesulfonate, p-toluene sulfonate, and methane sulfonate.
Thus, at least 70.0 mole%, preferably at least 80.0 mole%, preferably at least 85.0 mole%, preferably at least 90.0 mole%, more preferably at least 92.0 mole%, more preferably at least 94.0 mole% of the recurring units of polymer (P) are oxyethylene recurring units (EO).
It will also be appreciated that up to 99.0 mole%, more preferably up to 98.5 mole%, more preferably up to 98.0 mole% of the recurring units of polymer (P) are EO units.
In a preferred embodiment, the polymer (P) comprises at least 80.0 mol% and at most 99.0 mol%, preferably at least 90.0 mol% and at most 98.5 mol%, preferably at least 92.0 mol% and at most 98.5 mol% EO units, preferably at least 94.0 mol% and at most 98.5 mol% EO units.
When oxypropylene repeating units (PO) are present in polymer (P), up to 10.0 mole%, more preferably up to 6.0 mole%, even more preferably up to 5.0 mole%, even more preferably 4.0 mole%, even more preferably up to 3.0 mole% of the repeating units of polymer (P) are PO units.
Advantageously, the polymer (P) comprises at least 0.1 mol%, or at least 0.5 mol%, or at least 1.0 mol% PO units.
In a preferred embodiment, the polymer (P) comprises at least 0.5 mol% and at most 6.0 mol%, or at least 0.5 mol% and at most 5.0 mol%, or at least 0.5 mol% and at most 4.0 mol%, or at least 1.0 mol% and at most 3.0 mol% PO units.
The presence of PO units reduces the crystallinity of the polymer (P), which improves its ionic conductivity.
For the purposes of the present invention, the term "oxypropylene" (PO) is intended to mean a compound of the formula-0-CH 2 -CH 2 -CH 2 -or-0-CH 2 -CH(CH 3 ) -, preferably-O-CH 2 -CH(CH 3 )-。
Preferably, at least 1.2 mole%, or at least 1.5 mole%, or at least 1.8 mole%, or at least 2.2 mole% of the recurring units of the polymer (P) are recurring units derived from the monomer (M) of the general formula (I) or (II) as detailed above.
It is also understood that up to 4.0 mole%, more preferably up to 3.5 mole%, even more preferably up to 3.0 mole% of the recurring units of the polymer (P) are recurring units derived from the monomer (M) of the general formula (I) or (II) as detailed above.
In a preferred embodiment, the polymer (P) comprises at least 1.2 mol% and at most 4.0 mol%, preferably at least 1.5 mol% and at most 3.5 mol%, preferably at least 1.5 mol% and at most 3.0 mol% of recurring units derived from at least one monomer (M) of the general formula (I) or (II) as detailed above.
When the repeating unit in polymer (P) is derived from monomer (M) of formula (II), it is understood that the repeating unit is the result of ring opening polymerization of the epoxide moiety.
When the repeating unit in polymer (P) is derived from monomer (M) of formula (I) (wherein X is an acid chloride or an acid bromide), it is understood that the repeating unit may be the result of the following process: the monomer (M) reacts with terminal OH groups of EO units or PO units, such as dihydroxy-terminated polyethylene oxide (or PEO-co-PPO copolymer), thereby forming ester moieties.
When the repeating unit in the polymer (P) is derived from the monomer (M) of the general formula (I) (wherein X is trifluoromethanesulfonate, nonafluorobutanesulfonate, P-toluenesulfonate or methanesulfonate), the repeating unit may be the result of the following process: in the presence of a strong base, such as NaH, a wilhelmson type reaction occurs between the monomer (M) and terminal OH groups of EO units or PO units, such as dihydroxy-terminated polyethylene oxide (or PEO-co-PPO copolymer), thereby forming ether moieties. Via alkoxide formation and subsequent substitution of the X moiety of monomer (M).
These polymerizations are known in the art and are described in particular in Journal of Applied Polymer Science 2001,80,2446 by H.—Q.Xie, J.—S.Guo, G.—Q.Yu and J.Zu.
Preferably, each of X in the monomer (M) of formula (I) is a halide, more preferably a halide selected from chloride, bromide and iodide.
According to a preferred embodiment, the monomer (M) has the formula (II)
Wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-2 Alkanediyl, and n is an integer 0 or 1, preferably n is 1.
In another preferred embodiment of the positive electrode for a lithium ion secondary battery, the monomer (M) according to the invention is selected from those of formulae (Ia) to (If) and (IIa) to (IIe):
wherein X is selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluenesulfonate and methanesulfonate, acid chloride and acid bromide. Preferably X is a halide, more preferably a halide selected from chloride, bromide, iodide. Even more preferably X is bromide.
More preferably, the monomers (M) according to the invention are compounds selected from those of formulae (Ia) to (If).
Most preferably, the monomer (M) is a compound of formula (Ia).
According to a preferred embodiment of the positive electrode suitable for lithium ion secondary batteries, the polymer (P) consists essentially of:
a) 94.0 to 98.5 mole% EO repeat units;
b) 0.5 to 3.0 mole% of PO repeat units; and
c) 1.0 to 3.0 mol% of recurring units derived from monomer (M) of the general formula (II):
wherein R is 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-2 Alkanediyl, and n is an integer 0 or 1, preferably n is 1. It will be appreciated that chain defects or very small amounts of other units may be present, it being understood that these latter do not substantially modify the properties of the polymer (P).
Preferably, the polymer (P) as detailed above has a Mw (weight average molecular weight) of at least 10 g/mol, more preferably at least 20 g/mol, even more preferably at least 40 g/mol, even more preferably at least 50 g/mol.
It will be appreciated that the polymer (P) as detailed above preferably has a Mw of at most 150000g/mol, more preferably at most 100 g/mol.
In a preferred embodiment, the polymer (P) as detailed above has a Mw of at least 10 and at most 150 g/mol, preferably at least 20 and at most 150000g/mol, more preferably at least 40 and at most 100 g/mol, even more preferably at least 50 and at most 100 g/mol.
According to the invention, mw is measured by GPC with PEO standard corrections. Thus, the Mw mentioned is the PEO equivalent.
Alternatively and even preferably, the polymer (P) as detailed above has a Mn (number average molecular weight) of at least 10 g/mol, more preferably at least 20 g/mol, even more preferably at least 40 g/mol, even more preferably at least 50 g/mol.
It will be appreciated that the polymer (P) as detailed above preferably has a Mn of at most 150000g/mol, more preferably at most 100 g/mol.
In a preferred embodiment, the polymer (P) as detailed above has a Mn of at least 10 and at most 150 g/mol, preferably at least 20 and at most 150000g/mol, more preferably at least 40 and at most 100 g/mol, even more preferably at least 50 and at most 100 g/mol.
According to the invention, mn is measured by GPC with correction of PEO standard. Thus, the Mn mentioned is the PEO equivalent.
Preferably, the polymer (P) according to the invention is a random or block copolymer, more preferably a random copolymer.
Preferably, the polymer (P) according to the invention is linear or branched, more preferably linear.
Particularly preferred polymers (P) are linear random copolymers, wherein it is notable that the backbone can be depicted according to formula (IV):
Wherein the ratio of o to q (o/q) in formula (IV) of the polymer (P) is between 25 and 100, or between 35 and 75, or between 40 and 60. The ratio of P to q (P/q) in formula (IV) of polymer (P) is advantageously between 0.05 and 1.50, preferably between 0.10 and 1.00, preferably between 0.20 and 0.60.
Notably, such polymers (P) are available under the trade nameThe CP-A series is commercially available from Meisei Chemical works ltd.
As mentioned, polysiloxane compounds having the formula (III),
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 Alkyl and hydroxy protecting groups, and
-m is an integer of at least 3;
-ch=ch by monomer (M) 2 At least a part of the moieties is grafted onto the polymer (P) as detailed above by reaction with H-Si moieties of the polysiloxane compound of formula (III).
Preferably, R 3 And R is 4 Each of which are identical or different from each other and are, independently at each occurrence, C 1-6 Alkyl, more preferably R 3 And R is 4 Each of which are identical or different from each other and are in each case methyl, ethyl, propyl or isopropyl, even more preferably R 3 And R is 4 Are identical or different from each other and are methyl at each occurrence.
Preferably, R 5 And R is 6 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-4 Alkyl or phenyl, wherein the C 1-4 Alkyl is optionally selected from halide, C 1-4 Alkyl or CF 3 Is substituted with one or more substituents, more preferably R 5 And R is 6 Each of which are identical or different from each other and are in each case methyl, ethyl, propyl or isopropyl, even more preferably R 5 And R is 6 Are identical or different from each other and are methyl at each occurrence.
Preferably, each R 7 Is C 1-6 Alkyl, more preferably, each R 7 Is C 1-4 Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
Preferably, m is an integer of at least 5, more preferably at least 7, even more preferably at least 8.
It should also be understood that m is preferably an integer of at most 1000, more preferably at most 500, even more preferably at most 100, even more preferably at most 20, even more preferably at most 15.
In a preferred embodiment of the invention, m is an integer of at least 5 and at most 1000, preferably at least 5 and at most 500, more preferably at least 5 and at most 100, even more preferably at least 5 and at most 20, even more preferably at least 7 and at most 20, even more preferably at least 8 and at most 15.
In the context of the present invention, it is to be understood that-ch=ch of monomer (M) 2 The moiety is capable of reacting with the H-Si moiety of the polysiloxane compound of formula (III) as detailed above, so as to obtain a covalent bond between the two moieties. Such reactions are commonly referred to as hydrosilylation reactions. It should also be appreciated that the reaction may involve one or more ofThe formation of intermediates, including metal complexes and sigma complexes.
-ch=ch for monomer (M) as detailed above 2 The reaction of at least a portion of the moieties with the H-Si moiety of the polysiloxane compound having formula (III) as detailed above can be successfully performed using several techniques known in the art.
Notably, the polymer (P) as detailed above and the polysiloxane having formula (III) as detailed above can be reacted significantly in the molten state; melt compounders such as extruders, melt kneaders or other devices may be advantageously used for this purpose.
Notably, the polymer (P) as detailed above and the polysiloxane having formula (III) as detailed above can be reacted in solution; according to this embodiment, the polymer (P) and the polysiloxane of formula (III) as detailed above are at least partially dissolved in a solvent. Dissolution may be obtained at room temperature or preferably at a reflux temperature of the solvent heated to at least 70 ℃, more preferably at least 80 ℃, even more preferably. The choice of solvent is not critical, provided that it is effective to solvate both the polymer (P) and the polysiloxane having formula (III) as detailed above, and does not interfere with the hydrosilylation reaction. In general, it is preferable to select an organic solvent. Among these organic solvents, benzene, toluene, xylene, cymene and the like are mentioned.
Furthermore, it is notable that the polymer (P) as detailed above and the polysiloxane of formula (III) as detailed above can be reacted in the presence of a catalyst, in particular a hydrosilylation catalyst.
Such hydrosilylation catalysts are known in the art. Catalysts based on ruthenium, platinum or rhodium, such as in particular Karstedt's catalyst, wilkinson's catalyst, speier's catalyst and mixtures thereof, are notable.
In the context of the present invention, the expression "through-ch=ch of monomer (M)" 2 By reaction of at least part of (C) with the H-Si moiety of the polysiloxane compound of formula (III) is meant monomersCh=ch of (M) 2 Only a part or all of which may react with the H-Si moiety of the polysiloxane compound having formula (III).
Preferably, the-ch=ch of monomer (M) is present by at least 10 mole%, more preferably at least 15 mole%, even more preferably at least 20 mole%, even more preferably at least 25 mole%, even more preferably at least 30 mole%, even more preferably at least 35 mole%, even more preferably at least 40 mole%, even more preferably at least 45 mole% 2 Part of which reacts with the H-Si part of the polysiloxane compound of formula (III), said polysiloxane compound of formula (III) as detailed above being grafted onto the polymer (P) as detailed above.
It will also be appreciated that up to 100 mole%, more preferably up to 95 mole%, even more preferably up to 90 mole%, even more preferably up to 85 mole%, even more preferably up to 80 mole%, even more preferably up to 75 mole%, even more preferably up to 70 mole%, even more preferably up to 65 mole%, even more preferably up to 60 mole% of the monomer (M) of-ch=ch can be passed 2 Part of which reacts with the H-Si part of the polysiloxane compound of formula (III), the polysiloxane compound of formula (III) as described in detail above being grafted onto the polymer (P) as described in detail above.
In a preferred embodiment, the at least 10 mol% and at most 90 mol%, more preferably at least 30 mol% and at most 70 mol%, even more preferably at least 40 mol% and at most 60 mol% of the monomer (M) is-ch=ch 2 Part of which reacts with the H-Si part of the polysiloxane compound of formula (III), said polysiloxane compound of formula (III) as detailed above being grafted onto the polymer (P) as detailed above.
The reaction can be monitored by using known analytical methods, such as in particular by using GPC or 1 H-NMR methods, as described in the experimental section.
Preferably, the polymer electrolyte is obtained by a reaction between: the at least one polymer (P) and at least 6 wt% or at least 7 wt% or at least 8 wt% of the at least one polysiloxane compound relative to the total amount of the at least one polymer (P) and the at least one polysiloxane compound.
Preferably, the polymer electrolyte is obtained by a reaction between: the at least one polymer (P) and at most 27 wt% or at most 25 wt% or at most 22 wt% of the at least one polysiloxane compound relative to the total amount of the at least one polymer (P) and the at least one polysiloxane compound.
In a preferred embodiment, the polymer electrolyte is obtained by a reaction between: the at least one polymer (P) and at least 6 wt% and at most 27 wt% or at least 7 wt% and at most 25 wt% or at least 8 wt% and at most 22 wt% of the at least one polysiloxane compound relative to the total amount of the at least one polymer (P) and the at least one polysiloxane compound.
As described above, a positive electrode for a lithium ion secondary battery comprises a positive electrode active material comprising at least an element selected from Li, M ', and oxygen, and at least one polymer electrolyte, wherein the metal M' has the formula: ni (Ni) 1-x-y-z Mn x Co y A z Wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40, and 0.00.ltoreq.z.ltoreq.0.10, as measured by ICP, wherein when A is present, A is different from Ni, mn, co and Li, and is preferably at least one of: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between: preferably, a is Al with an atomic ratio of a to the total amount of Ni, mn and/or Co higher than 0, preferably higher than 0.001, more preferably higher than 0.003, most preferably higher than 0.006. Preferably, a is Al with an atomic ratio of a to the total amount of Ni, mn and/or Co of less than 0.1, preferably less than 0.05, more preferably less than 0.01, most preferably less than 0.008. Preferably, A is Al, the atomic ratio of A to the total amount of Ni, mn and/or Co being in the range of 0.001-0.1, preferably in the range of 0.002-0.05, more preferably in the range of 0.003-0.01, most preferably in the range of 0.006-0.008.
According to certain embodiments of the positive electrode according to the invention, in the positive electrode according to the invention, the weight ratio of the polymer electrolyte to the positive electrode active material is at least 5%, more preferably at least 10%, even more preferably at least 15%.
Preferably, the weight ratio of polymer electrolyte to positive electrode active material in the positive electrode according to the invention is at most 50%, more preferably at most 30%, even more preferably at most 25%.
In a preferred embodiment, the weight ratio of the polymer electrolyte to the positive electrode active material in the positive electrode according to the present invention is 5% to 50%, preferably 10% to 30%, and more preferably 15% to 25%. Alternatively, the weight ratio of the polymer electrolyte to the positive electrode active material in the positive electrode according to the present invention is 5% to 50%, preferably 20% to 45%, and more preferably 30% to 40%.
In a preferred embodiment of the positive electrode of the present invention, the positive electrode comprises a polymer electrolyte as described above, a positive electrode active material as detailed above, and further comprises at least one lithium salt (Li salt) selected from the group consisting of: liTFSI, liFSI, liPF 6 、LiBF 4 And LiClO 4 . Such positive electrodes are defined as catholyte. Optionally, the Li salt is present in the positive electrode at 60:40 to 80:20 by weight, more preferably at 70:30 to 75:25 by weight of polymer electrolyte.
In a preferred embodiment of the positive electrode according to the present invention, the [ weight ratio×100] of the Li salt to the polymer electrolyte in the positive electrode according to the present invention is 5% to 50%, preferably 20% to 45%, and more preferably 30% to 40%.
In another preferred embodiment, the Li salt is LiTFSI.
Preferably, the positive electrode active material as detailed above is a particulate material, in particular a powder.
Battery and electrochemical cell
In another aspect, the present invention provides a polymer battery comprising a positive electrode according to the first aspect of the invention.
In another aspect, the present invention provides an electrochemical cell comprising a positive electrode according to the first aspect of the invention.
In another aspect, the invention provides the use of a positive electrode according to the invention in a battery.
In a final aspect, the present invention provides a battery or electrochemical cell comprising a positive electrode active material and a polymer electrolyte, the positive electrode active material comprising at least Li, M 'and an oxygen element, wherein M' consists of Ni, mn, co and A, the positive electrode material having a (1-x-y-z): (x+y+z) Ni (Mn+Co+A) molar ratio of 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40 and 0.00.ltoreq.z.ltoreq.0.10, wherein when A is present, A is different from Ni, mn, co and Li, and preferably is at least one of Al or: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
a) At least 70.0 mole% of oxyethylene units (EO);
b) 0.0 to 10.0 mole% oxypropylene units (PO); and
c) 1.00 to 4.0 mol% of recurring units derived from at least one monomer of the general formula (I) or (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is one or more substituents of (2)Substituted, and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
One embodiment of the invention is a battery or electrochemical cell comprising a positive electrode active material comprising Ni, mn, co, and A, and a polymer electrolyte, the positive electrode material having a Ni (Mn+Co+A) molar ratio of (1-x-y-z): (x+y+z), as measured by ICP, wherein 0.00.ltoreq.x.ltoreq.0.70, 0.00.ltoreq.y.ltoreq.0.40, and 0.00.ltoreq.z.ltoreq.0.10, wherein when A is present, A is different from Ni, mn, co, and Li, and preferably Al or at least one of: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
a) At least 70.0 mole% of oxyethylene units (EO);
b) 0.0 to 10.0 mole% oxypropylene units (PO); and
c) 1.00 to 4.0 mol% of recurring units derived from at least one monomer of the general formula (I) or (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
In a preferred embodiment, the battery is a lithium ion battery.
In a preferred embodiment, the cell or electrochemical cell of the present invention comprises a polymer electrolyte, as described in the positive electrode section provided above.
Examples and comparative examples
The following examples are intended to further illustrate the invention and are not intended to limit the scope of the invention.
1.1. Materials and methods
The following materials were used as described below, unless otherwise indicated.
Random polymer (P) was purchased from Meisei Chemical works ltd under the trade name CP series CP-A. Alternatively, the polymer (P) may be prepared by following the procedure disclosed in h. -q.xie, j. -s.guo, g. -q.yu and j.zu, journal of Applied Polymer Science 2001,80,2446.
Mono-hydride terminated polydimethyl siloxane (SiH terminated PDMS, M w =850 g/mol) from Gelest, inc.
Silica supported karsed-type catalysts were prepared according to q.j.miao, z. -p.fang and g.p.cai, catalysis Communications 2003,4,637-639.
LiTFSI (lithium bis (trifluoromethanesulfonyl) imide salt, based on 99.95% trace metals) was purchased from Sigma-Aldrich.
Anhydrous acetonitrile 99.8 wt% was purchased from Sigma-Aldrich.
Timcal Super P is a conductive Carbon black powder (CAS number 1333-86-4) manufactured by Imers Graphite & Carbon.
Polyethylene oxide (M with 1,000,000) w PEO) from Alfa Aesar.
Recording on a JEOL JNM ECZ 500MHz NMR spectrometer at room temperature 1 And H spectrum. Dissolving a polymer sample in CDCl 3 And optimizing the internal standard by using Tetramethylsilane (TMS).
Inductively Coupled Plasma (ICP) measurements were performed using an Agilent 720 ICP-OES (Agilent Technologies, https:// www.agilent.com/cs/library/brochures/5990-6497EN%20720-725_ICP-OES_LR. Pdf). A 1 gram sample of the powder was dissolved in 50mL of high purity hydrochloric acid (at least 37 wt% HCl relative to the total weight of the solution) in an erlenmeyer flask. The bottle may be covered with a petri dish and heated on a hot plate at 380 ℃ until the powder is completely dissolved. After cooling to room temperature, the solution in the conical flask was poured into a first 250mL volumetric flask. Thereafter, the first volumetric flask was filled with deionized water up to a 250mL scale, and then subjected to a complete homogenization process (1 st dilution). The appropriate amount of solution was removed from the first volumetric flask by pipette and transferred to a second 250mL volumetric flask for the 2 nd dilution, at which point the second volumetric flask was filled with internal standard element and 10% hydrochloric acid to a 250mL scale, and then homogenized. Finally, the solution was used for ICP measurement.
1.2. Polymer electrolyte preparation
Polymer (P), a random linear copolymer characterized in table 2, was reacted with a mono-hydride terminated polydimethylsiloxane (SiH terminated PDMS) by hydrosilylation according to the following procedure:
TABLE 2
| Polymer (P) | |
| Mol% of EO | 97.5％ |
| Mol% of PO | 0.5％ |
| Mol% of Allyl Glycidyl Ether (AGE) | 1.9％ |
| Mn (GPC corrected using PEO standard) | 72 000g/mol |
A mixture containing 2.0g of polymer (P) and 0.36g of SiH terminated PDMS was added to 50mL of benzene containing 20mg of a silica supported Karsted type catalyst and heated at 90℃for 48 hours under a nitrogen atmosphere. The heated mixture was filtered through celite to remove the solid catalyst, and then placed under reduced pressure to remove the solvent. -ch=ch through 50 mole% AGE units 2 Reaction with the H-Si portion of PDMS grafts PDMS onto polymer (P).
Successful grafting pass 1 H-NMR and GPC.
Polymer (P): 1 H-NMR(TMS，CDCl 3 500 MHz): delta (ppm) 1.2 (d, CH of PO units 3 ) 4 (m, AGE unit-OC 2 H-CH＝CH 2 ) 5.2 (m, C of AGE unit 2 H=ch-), 5.8 (m, AGE sheetmeta-CH＝CH 2 )。
Mono-hydride PDMS: 1 H-NMR(TMS，CDCl 3 ，500MHz)：δ(ppm)0.5(m，-Si-CH 2 -CH 2 -)，0.9(t，CH 3 -CH 2 -)，1.3(br，-Si-CH 2 -CH 2 -C 2 H-CH 3 )，4.8(m，H-Si-)。
polymer electrolyte: 1 H-NMR(TMS，CDCl 3 500 MHz): delta (ppm): 0.5 (br, PDMS-Si-C)H 2 -CH 2 (-), 0.9 (br, C of PDMS) H 3 -CH 2 (-), 1.1 (d, CH of PO units) 3 ) 1.2 (br, PDMS-Si-CH) 2 -CH 2 -C 2 H-CH 3 )，1.4(br，-OCH 2 -C 2 H-CH 2 -Si-)。
In a polyelectrolyte 1 In the H-NMR spectrum, the presence of a broad peak at 1.4ppm and the absence of a peak attributed to H-Si confirmed successful hydrosilylation.
Fig. 1 shows GPC elution curves of the polymer electrolyte, polymer (P), and polysiloxane prepared as above.
The elution time of the polymer electrolyte was shorter than that of the polymer (P), which indicates that the polymer electrolyte has a higher molecular weight than the polymer (P), and thus PDMS was successfully grafted onto the polymer (P).
The resulting polymer electrolyte was labeled PE1.
1.3. Preparation of positive electrode active material 1 (AM 1)
Lithium transition metal composite oxide having the general formula Li was prepared as a positive electrode active material according to the following method 1.010 (Ni 0.621 Mn 0.224 Co 0.155 ) 0.990 O 2.00 As measured by ICP:
step 1) preparation of transition metal oxidized hydroxide precursor: nickel-based preparation by a co-precipitation process in a large Continuous Stirred Tank Reactor (CSTR) with mixed nickel manganese cobalt sulfate, sodium hydroxide and ammoniaTransition metal oxidized hydroxide powder (TMH 2) having a metal composition of Ni 0.621 Mn 0.224 Co 0.155 As measured by ICP.
Step 2) first mixing: mixing TMH1 prepared by step 1) with Li 2 CO 3 Mixing in an industrial blender to obtain a first mixture having a lithium to metal ratio of 0.85.
Step 3) first roasting: the first mixture from step 2) was calcined at 900 ℃ for 10 hours in a dry air atmosphere to obtain a first calcined cake. The first calcined cake is crushed to obtain a first calcined powder.
Step 4) second mixing: the first calcined powder from step 3) was mixed with LiOH in an industrial blender to obtain a second mixture with a lithium to metal ratio of 1.01.
Step 5) second roasting: the second mixture of step 4) was calcined in dry air at 930 ℃ for 10 hours, followed by a pulverizing (bead milling) and sieving process to obtain a second calcined powder.
Step 6) third mixing: the second calcined powder from step 5) was mixed with LiOH at 1.5 mole% relative to the total molar content of Ni, mn and Co in an industrial blender to obtain a third mixture.
Step 7) third roasting: the third mixture from step 6) was calcined in dry air at 750 ℃ for 10 hours to obtain AM1.
1.4. Preparation of positive electrode EX1
Positive electrodes comprising PE1 and AM1 were prepared according to the following procedure:
step 1) a polymer electrolyte solution was prepared comprising a 99.8 wt% anhydrous acetonitrile solution of the polymer electrolytes PE1 and LiTFSI. The polymer electrolyte solution has a polymer electrolyte to LiTFSI ratio of 74:26 by weight. This weight ratio corresponds to 35% LiTFSI polymer electrolyte [ weight ratio X100 ].
Step 2) the polymer electrolyte solution prepared in step 1), the positive electrode active material AM1 prepared according to part 1.2, and carbon black powder (Timcal Super carbon black) were mixed in an acetonitrile solution at a ratio of 21:75:4 by weight, so as to prepare a slurry mixture. The mixing was carried out by means of a homogenizer at 5000rpm for 45 minutes.
Step 3) the slurry mixture from step 2) was cast on one side of a 20 μm thick aluminum foil with a coater gap of 100 μm.
Step 4) the slurry-cast foil was dried at 30 ℃ for 12 hours and then punched to obtain a positive electrode having a diameter of 14 mm.
The positive electrode is labeled EX1.
1.5. Preparation of positive electrode active material 2 (AM 2)
The positive electrode active material AM2 was prepared according to the following procedure:
step 1) preparation of transition metal oxidized hydroxide precursor: nickel-based transition metal oxidized hydroxide powder (TMH 1) having a metal composition of Ni is prepared by a co-precipitation process in a large Continuous Stirred Tank Reactor (CSTR) with mixed nickel manganese cobalt sulfate, sodium hydroxide and ammonia 0.63 Mn 0.22 Co 0.15 As measured by ICP.
Step 2) first mixing: mixing TMH1 prepared by step 1) with Li 2 CO 3 Mixing in an industrial blender to obtain a first mixture having a lithium to metal ratio of 0.85.
Step 3) first roasting: the first mixture from step 2) was calcined at 900 ℃ for 10 hours in a dry air atmosphere to obtain a first calcined cake. The first calcined cake is crushed to obtain a first calcined powder.
Step 4) second mixing: the first calcined powder from step 3) was mixed with LiOH in an industrial blender to obtain a second mixture with a lithium to metal ratio of 1.05.
Step 5) second roasting: the second mixture of step 4) was calcined in dry air at 930 ℃ for 10 hours, followed by a pulverizing (bead milling) and sieving process to obtain a second calcined powder.
Step 6) third mixing: combining the second calcined powder from step 5) with a metal oxide based on Ni, mn and/or MnCo is present in a total molar content of 2 mole% Co (e.g., from Co 3 O 4 Powder) and 5 mole% LiOH were mixed in an industrial blender to obtain a third mixture.
Step 7) third roasting: the third mixture from step 6) was calcined in dry air at 775 ℃ for 12 hours to produce a third calcined powder.
Step 8) fourth mixing: mixing the third calcined powder from step 7) with 0.2 wt.% nano Al 2 O 3 Mixing the powder.
Step 9) fourth roasting: the fourth mixture from step 8) was calcined in dry air at 750 ℃ for 10 hours to produce a fourth calcined powder.
Step 10) fifth mixing: the fourth calcined powder from step 9) was mixed with 0.3 wt% polyvinylidene fluoride (PVDF).
Step 11) fifth roasting: the fifth mixture from step 10) was calcined in dry air at 375 ℃ for 5 hours to produce AM2.
1.6. Preparation of positive electrode EX2
Positive electrodes comprising AM2 and PE1 were prepared according to the following procedure:
step 1) a polymer electrolyte solution was prepared comprising a 99.8 wt% anhydrous acetonitrile solution of the polymer electrolytes PE1 and LiTFSI. The polymer electrolyte solution has a polymer electrolyte to LiTFSI ratio of 74:26 by weight.
Step 2) the polymer electrolyte solution prepared in step 1), the positive electrode active material AM2, and carbon black powder (Timcal Super carbon black) were mixed in an acetonitrile solution at a ratio of 21:75:4 by weight, so as to prepare a slurry mixture. The mixing was carried out by means of a homogenizer at 5000rpm for 45 minutes.
Step 3) the slurry mixture from step 2) was cast on one side of a 20 μm thick aluminum foil with a coater gap of 100 μm.
Step 4) the slurry-cast foil was dried at 30 ℃ for 12 hours and then punched to obtain a positive electrode having a diameter of 14 mm.
The positive electrode is labeled EX2.
1.7. Positive electrode CEX1 preparation
Positive electrodes comprising PE2 (poly (ethylene oxide) (PEO) powder (Mw 1,000,000 g/mol) from Alfa Aesar) and AM1 were prepared according to the following procedure:
step 1) a polymer electrolyte solution was prepared comprising a 99.8 wt% anhydrous acetonitrile solution of polymer electrolyte (PE 2) and LiTFSI. The polymer electrolyte solution has a polymer electrolyte to LiTFSI ratio of 74:26 by weight.
Step 2) the polymer electrolyte mixture prepared in step 1), the positive electrode active material AM1, and a conductor powder (Super P, timcal (imalys Graphite & Carbon) were mixed in an acetonitrile solution at a ratio of 21:75:4 by weight, so as to prepare a slurry mixture. The mixing was carried out by means of a homogenizer at 5000rpm for 45 minutes.
Step 3) the slurry mixture from step 2) was cast on one side of a 20 μm thick aluminum foil with a coater gap of 100 μm.
Step 4) the slurry-cast foil was dried at 30 ℃ for 12 hours and then punched to obtain a positive electrode having a diameter of 14 mm.
The positive electrode is labeled CEX1.
1.8. Solid Polymer Electrolyte (SPE) preparation
PEO-based Solid Polymer Electrolytes (SPEs) were prepared according to the following procedure:
step 1) polyethylene oxide (PEO, molecular weight 1,000,000) was mixed with LiTFSI (ex Soulbrain co., ltd. Instead of Sigma Aldrich) in 99.8 wt% anhydrous acetonitrile using a mixer at 2,000 revolutions per minute (rpm) for 30 minutes. The molar ratio of ethylene oxide to lithium was 20.
Step 2) the mixture from step 1) was poured into a Teflon dish and dried at 25 ℃ for 12 hours.
Step 3) the dried SPE was separated from the dish and punched to obtain SPE discs with a thickness of 300 μm and a diameter of 19 mm.
1.9. Polymer battery assembly
Button polymer cells were assembled in bottom-to-top order in an argon filled glove box: 2032 button cell casing, positive electrode (EX 1, EX2 or CEX 1), chapter by section
1.8 SPE, gasket, li anode, spacer, wave spring and battery cover. The coin cell was then fully sealed to prevent electrolyte leakage.
Total (S) 2. Comparison and test method (Q)
The leakage capacities of EX1, EX2 and CEX1 were measured (Q Total (S) )。
Each button-type polymer cell was cycled at 80℃using a Toscat-3100 computer-controlled constant current cycling station (available from Toyo, http:// www.toyosystem.com/image/menu3/Toscat/TOSCAT-3100. Pdf). Coin cell testing procedures were performed according to the following schedule using a 1C current definition of 160mA/g over a 4.4V/Li-3.0V/Li metal window:
step 1) was charged in a constant current mode with a C rate of 0.05 and an end condition of 4.4V, and then left to stand for 10 minutes.
Step 2) discharge in constant current mode with a C rate of 0.05 and an end condition of 3.0V, and then stand for 10 minutes.
Step 3) charging in constant current mode, C rate of 0.05, and end condition of 4.4V.
Step 4) was switched to constant voltage mode and held at 4.4V for 60 hours.
Step 5) discharge in constant current mode with a C rate of 0.05 and an end condition of 3.0V.
Q Total (S) Is defined as the total leakage capacity at high voltage and high temperature in step 4) according to the test method. Q (Q) Total (S) A low value indicates high stability of the positive electrode active material powder during high temperature operation.
TABLE 3 summary of positive electrode information for examples and comparative examples
| Positive electrode ID | Positive electrode active material ID | Polymer electrolyte ID |
| EX1 | AM1 | PE1 |
| EX2 | AM2 | PE1 |
| CEX1 | AM1 | PE2(PEO) |
TABLE 4 ICP results for positive electrode active materials
a Me is the total atomic fraction of Ni+Mn+Co+Al, as determined by ICP measurement
Total (S) Table 5. Summary of Q for examples and comparative examples.
FIG. 2 shows the polymer electrolyte pair Q according to the present invention Total (S) Influence of the value. The X-axis represents the polymer electrolyte used in the positive electrode. Legends indicate the positive electrode active materials used.
According to Table 5 and FIG. 2, EX1 was observed to have a lower Q than CEX1 Total (S) . This observation shows that a positive electrode comprising a combination of a positive electrode active material according to the invention and a polymer electrolyte provides better electrochemical performance than a combination with PEO as a conventional electrolyte. In addition, when PE1 is used as the polymer electrolyte, the surface-modified positive electrode active material powder (EX 2) according to the present invention has better electrochemical properties than EX 1. Q (Q) Total (S) A low value indicates high stability of the lithium ion secondary battery in applications where high voltage is applied at high temperature.
3. Characterization of Polymer electrolyte and Positive electrode Material contained in Positive electrode
The solid polymer electrolyte and the positive electrode material may be separated from each other by: the solid polymer electrolyte is selectively dissolved in a solvent such as DMSO, DMF, or acetonitrile, followed by separation of a liquid phase containing the solid polymer electrolyte and a solid component containing the positive electrode material by filtration or centrifugation. Drying of the liquid phase gives a solid polymer electrolyte, which can be characterized by NMR spectroscopy, as described in example 1.2. Optionally, the solid polymer electrolyte needs to be purified by precipitation in a non-solvent such as hexane or cyclohexane, followed by filtration and drying. ICP analysis of the solid component will reveal that the solid component comprises a metal composition as determined for AM1 or AM2, respectively, in table 4.
Claims (15)
1. A positive electrode for a lithium ion secondary battery, the positive electrode comprising a positive electrode active material and at least one polymer electrolyte, the positive electrode active material comprising Ni, mn, co and a, the positive electrode material having a molar ratio of Ni (mn+co+a) of (1-x-y-z): (x+y+z) measured by ICP, wherein 0.00 +.x +.0.70, 0.00 +.y +.0.40 and 0.00 +.z +.0.10, wherein when a is present, a is different from Ni, mn, co and Li, and preferably Al or at least one of: B. mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by a reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
-at least 70.0 mole% of oxyethylene units (EO);
-0.0 to 10.0 mol% oxypropylene units (PO); and
-1.00 to 4.0 mol% of recurring units derived from at least one monomer of formula (I) or formula (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy group,The heterocyclic groups optionally being selected from halogen ions, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein-ch=ch by monomer (M) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
2. The positive electrode according to claim 1, wherein 80.0 to 99.0 mol%, preferably 90.0 to 98.5 mol%, preferably 92.0 to 98.5 mol%, preferably 94.0 to 98.5 mol% of the recurring units of the polymer (P) are EO units.
3. The positive electrode according to claim 1 or claim 2, wherein 0.5 to 6.0 mol%, or 0.5 to 5.0 mol%, or 0.5 to 4.0 mol%, or 1.0 to 3.0 mol% of the recurring units of the polymer (P) are PO units.
4. The positive electrode according to any one of the preceding claims, wherein 1.2 to 4.0 mol%, or 1.5 to 3.5 mol%, or 1.5 to 3.0 mol% of the recurring units of the polymer (P) are recurring units derived from a monomer (M) of formula (I) or formula (II), wherein R 1 、R 2 N and X are the same as defined in claim 1.
5. The positive electrode according to any one of the preceding claims, wherein the monomer (M) has formula (II)
Wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-2 Alkanediyl, and n is an integer 0 or 1, preferably n is 1.
6. The positive electrode according to any one of the preceding claims, wherein R 3 、R 4 And R is 7 Each of which are identical or different from each other and are, independently at each occurrence, C 1-6 An alkyl group; r is R 5 And R is 6 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-4 Alkyl or phenyl, wherein the C 1-4 Alkyl is optionally selected from halide, C 1-4 Alkyl or CF 3 Is substituted with one or more substituents; m is an integer of at least 5 and at most 1000, preferably at least 5 and at most 500, more preferably at least 5 and at most 100, even more preferably at least 5 and at most 20, even more preferably at least 7 and at most 20, even more preferably at least 8 and at most 15.
7. The positive electrode according to any one of the preceding claims, wherein-ch=ch of the monomer (M) by at least 10 mol% and at most 90 mol%, more preferably at least 30 mol% and at most 70 mol%, even more preferably at least 40 mol% and at most 60 mol% 2 Reaction of the moiety with the H-Si moiety of the polysiloxane compound of formula (III), which is grafted onto the polymer (P).
8. The positive electrode according to any one of the preceding claims, wherein the weight ratio of the polymer electrolyte to the positive electrode active material is 5% to 50%, preferably 20% to 45%, and more preferably 30% to 40%.
9. The positive electrode according to any one of the preceding claims, wherein the positive electrodeThe electrode further comprises at least one lithium salt selected from the group consisting of: liTFSI, liFSI, liPF 6 、LiBF 4 And LiClO 4 。
10. The positive electrode according to any of the preceding claims, wherein a is Al and the atomic ratio of a to the total amount of Ni, mn and/or Co is higher than 0.
11. A polymer battery comprising the positive electrode according to any one of the preceding claims.
12. An electrochemical cell comprising the positive electrode according to any one of claims 1 to 10.
13. Use of the positive electrode according to any one of claims 1 to 10 in a battery.
14. A battery or electrochemical cell comprising a positive electrode active material comprising Ni, mn, co and a, the positive electrode material having a molar ratio of Ni (mn+co+a) of (1-x-y-z) measured by ICP, wherein 0.00 +.ltoreq.x +.0.70, 0.00 +.y +.0.40 and 0.00 +.z +.0.10, and a polymer electrolyte, wherein when a is present, a is different from at least one of Ni, mn, co and Li, preferably Al or B, mg, al, nb, ti, Y, W, S, ba, sr and Zr, and the polymer electrolyte is obtained by reaction between:
i. At least one polyether polymer [ polymer (P) hereinafter ], said polymer (P) comprising:
-at least 70.0 mole% of oxyethylene units (EO);
-0.0 to 10.0 mol% oxypropylene units (PO); and
-1.00 to 4.0 mol% of recurring units derived from at least one monomer of formula (I) or formula (II) [ monomer (M) hereinafter) ]:
wherein the method comprises the steps of
-R 1 And R is 2 Each of which are identical or different from each other and are C at each occurrence 1-6 Alkanediyl, wherein said C 1-6 Alkyldiyl is optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 8 Is substituted with one or more substituents of (2), and wherein each R 8 Are identical or different from each other and are independently selected at each occurrence from hydrogen and C 1-4 An alkyl group; n is an integer 0 or 1 or 2;
-each X is a leaving group selected from the group consisting of halide, trifluoromethane sulfonate, nonafluorobutane sulfonate, p-toluene sulfonate and methane sulfonate;
and
at least one polysiloxane compound having the formula (III):
wherein the method comprises the steps of
-R 3 、R 4 、R 5 、R 6 And R is 7 Each of which are the same or different from each other and are independently selected at each occurrence from C 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl, wherein C is 1-6 Alkyl, C 3-6 Cycloalkyl, aryl, C 1-6 Alkoxy, heterocyclyl are optionally selected from halide, C 1-4 Alkyl, C 3-6 Cycloalkyl, CF 3 、OR 9 Is substituted with one or more substituents of (2), and wherein each R 9 Are identical or different from each other and are independently selected at each occurrence from hydrogen, C 1-4 An alkyl group and a hydroxyl-protecting group,
-m is an integer of at least 3; and is also provided with
Wherein the monomer (M)) -ch=ch of (2) 2 Reaction of at least a part of the moieties with H-Si moieties of the polysiloxane compound of formula (III), the at least one polysiloxane compound of formula (III) being grafted onto the at least one polymer (P).
15. The battery or electrochemical cell of claim 14, comprising at least one lithium salt selected from the group consisting of: liTFSI, liFSI, liPF 6 、LiBF 4 And LiClO 4 。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20217310.0 | 2020-12-24 | ||
| EP20217310 | 2020-12-24 | ||
| EP20217309.2 | 2020-12-24 | ||
| PCT/EP2021/087507 WO2022136648A1 (en) | 2020-12-24 | 2021-12-23 | A positive electrode |
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| Publication Number | Publication Date |
|---|---|
| CN116868397A true CN116868397A (en) | 2023-10-10 |
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