CN118016888A - Positive electrode material and secondary battery comprising same - Google Patents
Positive electrode material and secondary battery comprising same Download PDFInfo
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- CN118016888A CN118016888A CN202410172224.4A CN202410172224A CN118016888A CN 118016888 A CN118016888 A CN 118016888A CN 202410172224 A CN202410172224 A CN 202410172224A CN 118016888 A CN118016888 A CN 118016888A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- -1 cyclic sulfate compound Chemical class 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 6
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- BWOVZCWSJFYBRM-UHFFFAOYSA-N carbononitridic isocyanate Chemical compound O=C=NC#N BWOVZCWSJFYBRM-UHFFFAOYSA-N 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002210 silicon-based material Substances 0.000 claims description 5
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229910001428 transition metal ion Inorganic materials 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241001514666 Kunzea Species 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HWBLTYHIEYOAOL-UHFFFAOYSA-N Diisopropyl sulfate Chemical compound CC(C)OS(=O)(=O)OC(C)C HWBLTYHIEYOAOL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910016096 LiMn0.5Fe0.5PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- OLRPCFUKOXRPBA-UHFFFAOYSA-N sulfosulfonyloxyethene Chemical group C=COS(=O)(=O)S(=O)(=O)O OLRPCFUKOXRPBA-UHFFFAOYSA-N 0.000 description 1
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material and a secondary battery comprising the same. The positive electrode material includes a positive electrode active material and a multi-ring cyclic sulfate compound additive. According to the invention, the annular sulfate additive with the multi-ring structure is introduced into the positive electrode material, so that the stability and the conductivity of the positive electrode material can be improved, a CEI film with high thermal stability can be formed on one side of the positive electrode, the gas generation of the battery can be inhibited, and the high-temperature storage and the cycle performance of the battery can be improved.
Description
Technical Field
The invention belongs to the technical field of additive materials, and particularly relates to a positive electrode material and a secondary battery containing the same.
Background
From the aspect of the cathode, the silicon-based cathode material is easy to generate huge volume change in the process of charging and discharging, and the conductivity of the silicon-based cathode material is reduced along with the silicon-based cathode material, so that the capacity of the battery is rapidly attenuated. Meanwhile, the silicon-based anode material is unstable in structure, is easy to react with electrolyte chemically and electrochemically, and has more obvious volume expansion phenomenon along with the continuous increase of silicon content, and the damage to the electrode material and the decomposition of the electrolyte are aggravated, so that the electric performance attenuation of the battery is accelerated.
From the positive electrode aspect, the positive electrode material tends to increase the nickel content of the structure, thereby increasing the energy density of the positive electrode. However, as the content of nickel is continuously increased, the sintering temperature of the cathode material is correspondingly lower in the preparation process, so that the residual quantity of alkaline impurities among particles is greatly increased, meanwhile, the structure of the cathode material is unstable, the cathode material is high in oxidizing property, side reactions with electrolyte are easy to occur, serious gas production phenomenon is caused in the charging and discharging processes of the battery, the volume of the battery is expanded, the cycle and the shelf life of the battery are shortened, and potential safety hazards are easy to exist.
In recent years, the prior art discloses the use of additives containing sulfur elements (e.g., vinyl sulfate) in an electrolyte to form an interface film having thermal stability on the surfaces of the positive and negative electrodes, thereby reducing side reactions between the electrodes and the electrolyte and improving the high temperature performance of the battery. However, on the one hand, the additive containing sulfur element mainly undergoes a reduction reaction on the surface of the negative electrode to form an inorganic solid electrolyte membrane (SEI membrane for short) without elasticity, and the SEI membrane is not easy to repair once broken, so that the SEI membrane is not suitable for a silicon-based material easy to expand in volume, and the continuous deterioration of the cycle performance of a silicon system is easily caused. On the other hand, because the additive containing sulfur is reduced in a large amount on the surface of the negative electrode, only a very small amount of the additive containing sulfur is reduced on the surface of the positive electrode to form a CEI film, the effect of the additive is greatly reduced, and the high-temperature performance of the whole battery is not obviously improved.
Accordingly, there is a need in the art to develop an additive material to address the above-described problems.
Disclosure of Invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a positive electrode material and a secondary battery including the same. According to the invention, the annular sulfate additive with the multi-ring structure is introduced into the positive electrode material, so that the stability and the conductivity of the positive electrode material can be improved, a CEI film with high thermal stability can be formed on one side of the positive electrode, the gas generation of the battery can be inhibited, and the high-temperature storage and the cycle performance of the battery can be improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode material comprising a positive electrode active material and a polycyclic cyclic sulfate compound additive.
In the present invention, "multi-ring" in "multi-ring cyclic sulfate compound additive" means a two-membered ring or more.
Aiming at the technical problems that the single-ring cyclic sulfate compound in the prior art has poor stability, is easy to decompose and has very little effect of improving gas production, meanwhile, the disclosed multi-ring cyclic sulfate compound mainly forms an SEI film without elasticity on the surface of a negative electrode, can not effectively form a film on the surface of a positive electrode, has poor effect of improving gas production and is not suitable for a silicon negative electrode material expansion system, the invention has the following technical effects by introducing the multi-ring cyclic sulfate compound into the positive electrode material:
firstly, from the aspect of battery preparation, the cyclic sulfate with the multi-ring structure has good stability, is not easy to decompose in the process of preparing the battery pole piece, and avoids gas production or other side effects of the battery. In addition, the cyclic sulfate with the multi-ring structure can neutralize residual alkali on the surface of the positive electrode material, and avoid the action of the binder and the residual alkali, so that the cohesiveness of the slurry is improved and the coating effect is improved;
Secondly, in terms of battery performance, on the one hand, the cyclic sulfate with the multi-ring structure can form a long-chain PEO polymer with electron donating ability on the surface of the positive electrode, so that lithium ion conduction can be promoted, and meanwhile, the long-chain PEO polymer with electron donating ability can be complexed with transition metal ions (such as Mn 2+、Fe2+ and other electron-deficient groups), so that dissolution of the transition metal ions is inhibited, and the conductivity and stability of the positive electrode are improved. In addition, the cyclic sulfate with the multi-ring structure effectively forms a CEI film (composed of RSO 3 Li and ROSO 2 Li) with high thermal stability on the surface of the positive electrode, so that the interface stability of the positive electrode/electrolyte can be further improved, the side reaction is reduced, the gas production is reduced, and the high-temperature performance of the battery can be improved;
On the other hand, the annular sulfate additive with the multi-ring structure is only consumed on the positive electrode side, cannot migrate to the negative electrode side through electrolyte, and cannot participate in the negative electrode film forming process, so that the deterioration of the circulating performance of the silicon negative electrode material caused by the formation of the sulfur-rich inorganic SEI film can be avoided, and meanwhile, the corrosion effect of sulfur components on the silicon negative electrode material can be avoided, so that the circulating performance of the battery is further improved;
In short, compared with the method of adding the cyclic sulfate with the multi-ring structure into the electrolyte, the technical effect of introducing the cyclic sulfate with the multi-ring structure into the positive electrode material is more remarkable.
Preferably, the polycyclic cyclic sulfate compound comprises a first compound having a structure represented by formula i and/or a second compound having a structure represented by formula ii:
wherein R 1、R2、R3、R4 is each independently selected from at least one of hydrogen, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C1-C6 alkoxy, keto, ester, amide, phosphate, borate, isocyanate, phenyl, siloxane, sulfonate, sulfonyl, substituted or unsubstituted sulfate.
In the present invention, the substituted or unsubstituted C1-C6 alkyl group means that the number of carbon atoms in the main chain is 1 to 6, and may be, for example, 1, 2, 3, 4, 5, 6.
In the present invention, substituted or unsubstituted C2-C6 alkenyl means that the number of carbon atoms in the main chain is 2 to 6, and may be, for example, 2, 3,4, 5, 6.
In the present invention, substituted or unsubstituted C2-C6 alkynyl means that the number of carbon atoms in the main chain is 2 to 6, and may be, for example, 2, 3,4, 5, 6.
In the present invention, the substituted or unsubstituted C1-C6 alkoxy group means that the number of carbon atoms in the main chain is 1 to 6, and may be, for example, 1,2, 3, 4, 5, 6.
Preferably, the substituted group comprises any one or a combination of at least two of halogen, cyano, isocyanate, phosphate, borate, sulfate and siloxane groups.
Further preferably, each R 1、R2、R3、R4 is independently selected from at least one of halogen, cyano, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted C1-C6 alkoxy, isocyanate, siloxane, sulfonate, substituted or unsubstituted sulfate.
In the invention, R 1、R2、R3、R4 is further optimized to enable the R 1-R4 group to be a group with electron withdrawing on a side chain (such as halogen, cyano, C2-C6 alkenyl, C2-C6 alkynyl, sulfonate group and the like), the electron withdrawing group enables the structure of the structural compound shown in the formula I or the formula II to be more stable, and a CEI film with high stability and high oxidation resistance is formed after the positive electrode participates in film formation, so that the stability of the positive electrode under high voltage is improved, the stability of the positive electrode is enhanced, further side reaction of the positive electrode under high voltage can be obviously inhibited, and the gas yield is reduced;
Or R 1-R4 is a group (such as cyano, isocyanate, siloxane, etc.) for stabilizing the positive electrode, wherein the stable positive electrode comprises a group which participates in film formation of the positive electrode or is complexed with the positive electrode (inhibits dissolution of transition metal ions) or has acid and water removal functions, so that the positive electrode can be kept stable.
Further preferably, the substituted group comprises any one or a combination of at least two of halogen, cyano, isocyanate, sulfate and siloxane groups.
In the invention, the substituent is a group with electron withdrawing (halogen, cyano, sulfate, and the like) by further optimizing the substituent group, on one hand, the electron withdrawing group can increase the stability of the R 1-R4 group and promote the formation of a CEI film with high oxidation resistance at the positive electrode;
or the substituent may be a group (cyano group, isocyanate group, siloxane group, etc.) that stabilizes the positive electrode, including a group that participates in film formation of the positive electrode or complexes with the positive electrode (inhibits elution of transition metal ions) or has an acid-removing and water-removing function, and can keep the positive electrode stable.
Preferably, the first compound having the structure shown in formula i is any one of the following compounds:
Preferably, the second compound having the structure shown in formula ii is any one of the following compounds:
preferably, the content of the polycyclic cyclic sulfate compound additive is 0.1% to 1.5%, preferably 0.3% to 1.0%, for example, may be 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc., based on 100% of the total mass of the positive electrode material.
In the invention, the stable interface film is formed on one side of the positive electrode by regulating and controlling the mass percentage of the additive of the multi-ring cyclic sulfate compound, the film can be incompletely formed when the content is too low, the action effect is poor, otherwise, the thick interface film with larger impedance can be formed by fully reacting on the positive electrode when the content is too high, and the lithium ion transmission is not facilitated.
Preferably, the positive electrode material further includes a conductive agent and a binder.
In the present invention, examples of the conductive agent may include conductive carbon black, acetylene black, carbon nanotubes, and the like; the binder may include, for example, polyvinylidene fluoride, etc., and the present invention is not particularly limited in the kind of the above-mentioned conductive agent and binder.
In a second aspect, the present invention provides a secondary battery comprising a positive electrode comprising the positive electrode material according to the first aspect, a negative electrode, an electrolyte, and a separator.
Preferably, the material of the negative electrode includes a silicon-based material.
Preferably, the silicon-based material comprises at least one of a silicon oxygen material or a silicon carbon material.
In the present invention, the silicon oxide material may be, for example, silicon oxide, or the like.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a positive electrode material, which has the following technical effects:
firstly, from the aspect of battery preparation, the cyclic sulfate with the multi-ring structure has good stability, is not easy to decompose in the process of preparing the battery pole piece, and avoids gas production or other side effects of the battery. In addition, the cyclic sulfate with the multi-ring structure can neutralize residual alkali on the surface of the positive electrode material, and avoid the action of the binder and the residual alkali, so that the cohesiveness of the slurry is improved and the coating effect is improved;
Secondly, in terms of battery performance, on the one hand, the cyclic sulfate with the multi-ring structure can form a long-chain PEO polymer with electron donating ability on the surface of the positive electrode, so that lithium ion conduction can be promoted, and meanwhile, the long-chain PEO polymer with electron donating ability can be complexed with transition metal ions (such as Mn 2+、Fe2+ and other electron-deficient groups), so that dissolution of the transition metal ions is inhibited, and the conductivity and stability of the positive electrode are improved. In addition, the cyclic sulfate with the multi-ring structure effectively forms a CEI film (composed of RSO 3 Li and ROSO 2 Li) with high thermal stability on the surface of the positive electrode, so that the interface stability of the positive electrode/electrolyte can be further improved, the side reaction is reduced, the gas production is reduced, and the high-temperature performance of the battery can be improved;
On the other hand, the annular sulfate additive with the multi-ring structure is only consumed on the positive electrode side, cannot migrate to the negative electrode side through electrolyte, and cannot participate in the negative electrode film forming process, so that the deterioration of the circulating performance of the silicon negative electrode material caused by the formation of the sulfur-rich inorganic SEI film can be avoided, and meanwhile, the corrosion effect of sulfur components on the silicon negative electrode material can be avoided, so that the circulating performance of the battery is further improved;
In short, compared with the method of adding the cyclic sulfate with the multi-ring structure into the electrolyte, the technical effect of introducing the cyclic sulfate with the multi-ring structure into the positive electrode material is more remarkable.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides a positive electrode material comprising, based on 100% of the total mass of the positive electrode material, liNi 90Co5.5Mn3.5Al1O2 positive electrode active material in an amount of 97.0% by mass, 0.5% of an i-2 cyclic sulfate compound additive (available from shanghai as new materials, inc., trade mark PT 108), 1.5% of Super P-conductive agent, and 1.0% of polyvinylidene fluoride binder.
The embodiment also provides the positive electrode material and a preparation method of the positive electrode plate, and the preparation method comprises the following steps:
mixing the components according to the formula amount, adding an N-methyl pyrrolidone solvent, uniformly mixing to obtain positive electrode slurry, coating the positive electrode slurry on the surface of a carbon-coated aluminum foil, drying, and slicing to obtain the positive electrode plate.
Example 2
The present example provides a positive electrode material comprising, based on 100% of the total mass of the positive electrode material, 95.2% of LiCoO 2 positive electrode active material, 0.3% of an i-17 cyclic sulfate compound additive (commercially available from Shanghai such as new materials, inc., trade mark PT 135), 2% of Super P conductive agent, and 2.5% of polyvinylidene fluoride binder.
The embodiment also provides the positive electrode material and a preparation method of the positive electrode plate, and the preparation method comprises the following steps:
mixing the components according to the formula amount, adding an N-methyl pyrrolidone solvent, uniformly mixing to obtain positive electrode slurry, coating the positive electrode slurry on the surface of a carbon-coated aluminum foil, drying, and slicing to obtain the positive electrode plate.
Example 3
The present example provides a positive electrode material comprising 94.6% by mass of LiMn 0.5Fe0.5PO4 positive electrode active material, 1.0% by mass of an i-12 cyclic sulfate compound additive (available from shanghai such as new materials inc., trade mark PT 121), 2.0% by mass of Super P conductive agent and 2.4% by mass of polyvinylidene fluoride binder, based on 100% by mass of the total positive electrode material.
The embodiment also provides the positive electrode material and a preparation method of the positive electrode plate, and the preparation method comprises the following steps:
mixing the components according to the formula amount, adding an N-methyl pyrrolidone solvent, uniformly mixing to obtain positive electrode slurry, coating the positive electrode slurry on the surface of a carbon-coated aluminum foil, drying, and slicing to obtain the positive electrode plate.
Example 4
This example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with I-12 (available from Shanghai such as Kunzea New Co., ltd., brand PT 121) and the other was identical to example 1.
Example 5
This example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with I-10 (available from Shanghai such as Kunzea materials Co., ltd., brand PT 117) and the other was identical to example 1.
Example 6
This example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with II-2 (available from Shanghai such as Kunzea materials Co., ltd., trade name PR 098) and the other was identical to example 1.
Example 7
This example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with II-12 (available from Shanghai such as Kunzea New Material Co., ltd., trade name PR 113), and the other was identical to example 1.
Example 8
This example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with vinyl dithionate, all other things being equal to example 1.
Example 9
The present example is different from example 1 in that the positive electrode material includes 97.40% by mass of LiNi 90Co5.5Mn3.5Al1O2 positive electrode active material, and 0.1% by mass of the i-2 cyclic sulfate compound additive, based on 100% by mass of the total positive electrode material, all of which are the same as example 1.
Example 10
The present example is different from example 1 in that the positive electrode material includes LiNi 90Co5.5Mn3.5Al1O2 positive electrode active material in an amount of 96.0% by mass, and the i-2 cyclic sulfate compound additive in an amount of 1.5% by mass, based on 100% by mass of the total positive electrode material, all of which are the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with an equal amount of vinyl sulfate, all other things being equal to example 1.
Comparative example 2
This comparative example differs from example 1 in that the I-2 cyclic sulfate compound additive was replaced with an equal amount of diisopropyl sulfate, all other things being equal to example 1.
Application examples 1-10 and comparative application examples 1-2
The positive electrode sheets provided in examples 1 to 10 and comparative examples 1 to 2 were assembled to obtain lithium ion batteries, and the preparation method was as follows:
positive plate: as previously described;
Negative electrode plate: mixing graphite, a silicon-oxygen composite material (model is S0210, purchased from Lanxi Zhiden New energy materials Co., ltd.), super P conductive agent, sodium carboxymethyl cellulose and styrene-butadiene latex according to the mass ratio of 85.6:9.5:1.2:3:0.6, adding deionized water, stirring to uniformly obtain negative electrode slurry, coating the negative electrode slurry on the surface of copper foil, drying, and slicing to obtain a negative electrode plate;
The positive plate, the negative plate, the electrolyte (the composition of the electrolyte is 12wt.% EC,12wt.% PC,52.5wt.% EMC,14.5wt.% LiPF 6,1wt.％LiPO2F2 and 8wt.% FEC) and the diaphragm are assembled to form batteries corresponding to all application examples, and then the batteries are formed at 45 ℃ (the formation steps are that 0.05C is charged to 3.0V, 0.1C is charged to 3.4V, and then 0.2C is charged to 3.7V), and aging and capacity division are carried out after the formation is completed, so that the lithium ion battery is obtained.
Comparative application example 3
Positive plate: mixing a LiNi 90Co5.5Mn3.5Al1O2 anode material, a Super P conductive agent and a polyvinylidene fluoride binder according to the mass ratio of 97.2:1.7:1.1, adding N-methyl pyrrolidone, uniformly stirring to obtain anode slurry, drying the anode slurry on the surface of a carbon-coated aluminum foil, and slicing to obtain an anode plate;
negative electrode plate: as previously described;
The positive plate, the negative plate, the electrolyte (the composition of the electrolyte is 12wt.% EC,12wt.% PC,52.0wt.% EMC,14.5wt.% LiPF 6,1wt.％LiPO2F2, 8wt.% FEC,0.5wt.% vinyl sulfate) and the diaphragm are assembled to obtain the battery, the battery is formed at 45 ℃, the battery is charged to 3.0V at 0.05C, charged to 3.4V at 0.1C and charged to 3.7V at 0.2C, and aging and capacity division are carried out after the formation is completed to obtain the lithium ion battery.
Comparative application example 4
Positive plate: mixing a LiNi 90Co5.5Mn3.5Al1O2 anode material, a Super P conductive agent and a polyvinylidene fluoride binder according to the mass ratio of 97.2:1.7:1.1, adding N-methyl pyrrolidone, uniformly stirring to obtain anode slurry, drying the anode slurry on the surface of a carbon-coated aluminum foil, and slicing to obtain an anode plate;
negative electrode plate: as previously described;
The positive plate, the negative plate, the electrolyte (12 wt.% of EC,12wt.% of PC,52.0wt.% of EMC,14.5wt.% of LiPF 6,1wt.％LiPO2F2, 8wt.% of FEC and 0.5wt.% of diisopropyl sulfate) and the diaphragm are assembled to obtain a battery, and then the battery is formed at 45 ℃ (the forming step is that 0.05C is charged to 3.0V, 0.1C is charged to 3.4V, and then 0.2C is charged to 3.7V), and aging and capacity division are carried out after the formation is completed to obtain the lithium ion battery.
Test conditions
The lithium ion batteries provided in application examples 1 to 10 and comparative application examples 1 to 4 were tested as follows:
(1) Gas production rate:
The battery volume testing method comprises the following steps: placing a beaker containing deionized water on an electronic balance, recording the indication m 1 of the electronic balance at the moment, fixing the battery in mid-air by using a clamp of an iron stand, slowly immersing the battery in the beaker containing ionized water downwards until the battery is completely immersed in the deionized water, recording the indication m 2 of the electronic balance at the moment, and calculating the volume (V) = (m 2-m1)×g/(ρH2O multiplied by P) of the battery according to the formula mg=ρ H2O VP. Where ρ H2O is the density of deionized water, g is the gravity coefficient, P is a standard atmospheric pressure, and V is the volume of the cell.
The battery before formation is subjected to the battery volume testing method and is brought into the battery volume formula to obtain the battery volume V 1 before formation; and then, the battery after the formation of each application example is also adopted by the battery volume testing method, and the formed battery volume V 2 can be obtained by taking the battery volume formula.
The gas yield of the battery of each application example was V 2-V1 at this time.
(2) High temperature cycle performance:
The lithium ion battery is placed in a 45 ℃ incubator, charged to 4.2V at constant current 1C, charged to 0.05C at constant voltage of 4.2V, and discharged to 2.8V at constant current 1C, which is recorded as a charge-discharge cycle process, and the initial discharge capacity is recorded. Capacity retention= (remaining discharge capacity/initial discharge capacity) ×100%. The number of battery cycles at 80% capacity retention was recorded.
(3) High temperature storage performance:
Charging the lithium ion battery to 4.2V at 25 ℃ with constant current of 1C, charging to 0.05C at constant voltage of 4.2V, and then discharging to 2.8V with constant current of 1C, which is recorded as a charge-discharge cycle process, recording initial discharge capacity C 0, placing the lithium ion battery in a 60 ℃ oven after full charge again, standing for 2h at normal temperature after storage for 30 days, discharging to 2.8V with 1C, recording the residual discharge capacity of the battery at the moment, and calculating to obtain the final battery capacity retention rate. Battery capacity retention= (remaining discharge capacity/initial discharge capacity) ×100%.
The test results are shown in table 1:
TABLE 1
As can be seen from table 1, it can be seen from application examples 1 to 4 that different positive electrodes differ in the selection of the kind of substituents in the cyclic sulfate compound additive, and the same kind of substituents have different effects in use in different positive electrode materials, for example, cyano group has a remarkable effect of complexing transition metal stable positive electrode in LiCoO 2, while in LiMn 0.5Fe0.5PO4 may mainly play a role in acid removal and water removal. For different types of positive electrode materials, the addition of the proper positive electrode additive into the positive electrode can effectively improve the high-temperature performance of the battery and inhibit gas production.
As can be seen from application examples 1 and 5, the cyclic sulfate compound additive shown in I-10 has excessive double bond substituents, and has remarkable effect of inhibiting gas generation, but increases internal impedance of the battery, so that lithium ion transmission is difficult, and cycle performance is reduced.
As can be seen from application example 1 and application examples 6 to 7, the effect of the cyclic sulfate compound having the structure shown in formula II is not as good as that of the cyclic sulfate compound having the structure shown in formula I.
It can be seen from application examples 1 and 9-10 that the introduction of the positive electrode additive with a smaller content is incomplete in film formation and poor in action effect, however, the positive electrode additive with an excessively high content is also harmful to lithium ion transmission due to thicker film formation and larger impedance, resulting in degradation of cycle performance in the battery.
As can be seen from application example 1 and comparative application examples 1-2, the linear sulfate and the monocyclic sulfate are inferior in effect because the fresh carbonate and the monocyclic sulfate are unstable themselves and are easily decomposed by heat, resulting in gas generation.
As can be seen from application example 1 and comparative application examples 3 to 4, the addition of the sulfate additive to the electrolyte has poor high-temperature storage and cycle performance, because the sulfate additive is easier to form a film on the negative electrode side, and the inorganic SEI film formed by mass consumption on the negative electrode side is easy to expand and crack during the silicon cycle, resulting in more side reactions and poorer cycle performance, and the positive electrode has less participation in film formation, incomplete film formation and poor effect, so that the high-temperature storage of the battery is poor.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A positive electrode material, characterized in that the positive electrode material comprises a positive electrode active material and a polycyclic cyclic sulfate compound additive.
2. The positive electrode material according to claim 1, wherein the polycyclic cyclic sulfate compound includes a first compound having a structure represented by formula i and/or a second compound having a structure represented by formula ii:
Wherein R 1、R2、R3、R4 is each independently selected from at least one of hydrogen, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C1-C6 alkoxy, keto, ester, amide, phosphate, borate, isocyanate, phenyl, siloxane, sulfonate, sulfonyl, substituted or unsubstituted sulfate;
The substituted group includes any one or a combination of at least two of halogen, cyano, isocyanate, phosphate, borate, sulfate and siloxane groups.
3. The positive electrode material according to claim 2, wherein each R 1、R2、R3、R4 is independently selected from at least one of halogen, cyano, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted C1-C6 alkoxy, isocyanate, siloxane, sulfonate, substituted or unsubstituted sulfate;
preferably, the substituted group comprises any one or a combination of at least two of halogen, cyano, isocyanate, sulfate and siloxane groups.
4. The positive electrode material according to any one of claims 2 to 3, wherein the first compound having a structure represented by formula i is any one of the following compounds:
5. The positive electrode material according to any one of claims 2 to 3, wherein the second compound having a structure represented by formula ii is any one of the following compounds:
6. The positive electrode material according to any one of claims 1 to 5, characterized in that the mass percentage of the polycyclic cyclic sulfate compound additive is 0.1% to 1.5%, preferably 0.3% to 1.0%, based on 100% of the total mass of the positive electrode material.
7. The positive electrode material according to any one of claims 1 to 6, further comprising a conductive agent and a binder.
8. A secondary battery, characterized in that the secondary battery comprises a positive electrode including the positive electrode material according to any one of claims 1 to 7, a negative electrode, an electrolyte, and a separator.
9. The secondary battery according to claim 8, wherein the material of the negative electrode includes a silicon-based material.
10. The secondary battery according to claim 8 or 9, wherein the silicon-based material includes at least one of a silicon oxygen material and a silicon carbon material.
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