CN117378059A - Positive electrode active material, preparation method thereof, positive electrode plate, secondary battery, battery module, battery pack and power utilization device - Google Patents
Positive electrode active material, preparation method thereof, positive electrode plate, secondary battery, battery module, battery pack and power utilization device Download PDFInfo
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- CN117378059A CN117378059A CN202180098462.XA CN202180098462A CN117378059A CN 117378059 A CN117378059 A CN 117378059A CN 202180098462 A CN202180098462 A CN 202180098462A CN 117378059 A CN117378059 A CN 117378059A
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- positive electrode
- active material
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- electrode active
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- 239000010405 anode material Substances 0.000 description 1
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- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- 230000010261 cell growth Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000000619 electron energy-loss spectrum Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
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- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 238000003921 particle size analysis Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
Abstract
The application provides a positive electrode active material with a core-shell structure, a preparation method thereof, a positive electrode plate, a secondary battery, a battery module, a battery pack and an electric device comprising the positive electrode active material, wherein the positive electrode active material comprises a core and a shell coating the core, and the core comprises Li 1+x Mn 1‑y A y P 1‑z R z O 4 The shell comprises a first coating layer coating the inner core, a second coating layer coating the first coating layer and a third coating layer coating the second coating layer, wherein the first coating layer comprises crystalline pyrophosphates Li a MP 2 O 7 And/or M b (P 2 O 7 ) c The crystalline pyrophosphates are electrically neutral; the second coating layer comprises crystalline phosphate XPO 4 The method comprises the steps of carrying out a first treatment on the surface of the The third coating layer is carbon.
Description
The application relates to the technical field of lithium batteries, in particular to an anode active material and a preparation method thereof, an anode plate containing the anode active material, a secondary battery, a battery module, a battery pack and an electric device.
Along with the rapid development of the new energy field, the lithium ion battery is widely applied to various large-scale power devices, energy storage systems and various consumer products by virtue of the advantages of excellent electrochemical performance, no memory effect, small environmental pollution and the like, and is particularly widely applied to the fields of new energy automobiles such as pure electric automobiles, hybrid electric automobiles and the like. The lithium manganese phosphate positive electrode active material has the advantages of high working voltage, wide raw material sources, small environmental pollution and the like, and is considered to be a positive electrode active material for a power lithium ion battery, which is hopeful to replace lithium iron phosphate.
However, in the prior art, the cycle performance, high-temperature storage performance and safety performance of the secondary battery using the lithium manganese phosphate positive electrode active material have not been comprehensively improved, which greatly limits the wider range of applications of the lithium manganese phosphate battery. Therefore, it is still desired to design a lithium manganese phosphate positive electrode active material having a high gram capacity, good cycle performance and safety performance.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object thereof is to provide a novel lithium manganese phosphate doped positive electrode active material having a core-shell structure, which enables a secondary battery using the positive electrode active material to have a high gram capacity, good cycle performance, and good safety performance.
In order to achieve the above object, a first aspect of the present application provides a positive electrode active material having a core-shell structure, which includes a core and a shell coating the core,
the chemical formula of the inner core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S;
the values of x, y and z satisfy the following condition: keeping the whole kernel electrically neutral;
the shell includes a first cladding layer that coats the inner core, a second cladding layer that coats the first cladding layer, and a third cladding layer that coats the second cladding layer, wherein,
the first coating layer comprises crystalline pyrophosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c Wherein, the method comprises the steps of, wherein,
0≤a≤2, 1.ltoreq.b.ltoreq.4, 1.ltoreq.c.ltoreq.6, the values of a, b and c satisfying the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c The electric neutrality is maintained and the electric power is controlled,
the crystalline pyrophosphates Li a MP 2 O 7 And M b (P 2 O 7 ) c Each M in (2) is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al,
the second coating layer comprises crystalline phosphate XPO 4 Wherein, X is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;
the third coating layer is carbon.
Crystalline, as used herein, means crystallinity above 50%, i.e., 50% -100%. A crystallinity of less than 50% is referred to as glassy. Crystalline pyrophosphates and crystalline phosphates as described herein have a crystallinity of 50% to 100%. The pyrophosphate and the phosphate with certain crystallinity are beneficial to fully playing the functions of preventing manganese from dissolving out and leading lithium ions of the phosphate coating and reducing interface side reactions of the pyrophosphate coating, and the pyrophosphate coating and the phosphate coating can be better subjected to lattice matching, so that tight combination between the coating and the coating can be realized.
According to the lithium manganese phosphate anode active material with the core-shell structure, the element A is doped at the manganese position of the lithium manganese phosphate, the doped lithium manganese phosphate inner core is obtained by doping the element R at the phosphorus position, and three layers of coating are sequentially carried out on the surface of the inner core, so that the novel lithium manganese phosphate anode active material with the core-shell structure is provided, and the anode active material is applied to a secondary battery, so that the high-temperature cycle performance, the cycle stability and the high-temperature storage performance of the secondary battery can be remarkably improved.
In any embodiment, the crystalline pyrophosphate in the first cladding layer has an interplanar spacing ranging from 0.293 to 0.470nm and an included angle of the crystal orientation (111) ranging from 18.00 ° -32.00 °; the crystal-state phosphate in the second coating layer has a interplanar spacing range of 0.244-0.425nm and an included angle of the crystal direction (111) of 20.00-37.00 degrees.
The first coating layer and the second coating layer in the positive electrode active material described in the present application each use crystalline substances, and their interplanar spacings and angles are within the above ranges. Therefore, the impurity phase in the coating layer can be effectively avoided, and the gram capacity, the cycle performance and the multiplying power performance of the material are improved.
In any embodiment, in the core, the ratio of y to 1-y is 1:10 to 1:1, alternatively 1:4 to 1:1. thereby, the cycle performance and the rate performance of the secondary battery are further improved.
In any embodiment, in the kernel, the ratio of z to 1-z is 1:999 to 1:9, alternatively 1:499 to 1:249. thereby, the cycle performance and the rate performance of the secondary battery are further improved.
In any embodiment, the carbon of the third coating layer is a mixture of SP2 morphology carbon and SP3 morphology carbon, optionally, the molar ratio of SP2 morphology carbon to SP3 morphology carbon is any value in the range of 0.1-10, optionally, any value in the range of 2.0-3.0.
The present application improves the overall performance of the secondary battery by limiting the molar ratio of SP 2-form carbon to SP 3-form carbon within the above-described range.
In any embodiment, the first cladding layer is present in an amount greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core; and/or
The second cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, more alternatively from 2 to 4 wt%, based on the weight of the core; and/or
The third cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, and more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core.
In the positive electrode active material with the core-shell structure, the cladding amount of the three-layer cladding layer is preferably within the above range, so that the inner core can be fully clad, and meanwhile, the dynamic performance and the safety performance of the secondary battery are further improved on the premise of not sacrificing the gram capacity of the positive electrode active material.
In any embodiment, the thickness of the first coating layer is 1-10nm; and/or
The thickness of the second coating layer is 2-15nm; and/or
The thickness of the third coating layer is 2-25nm.
In the application, when the thickness range of the first coating layer is 1-10nm, adverse effects on the dynamic performance of the material, which may be generated when the first coating layer is too thick, can be avoided, and the problem that migration of transition metal ions cannot be effectively blocked when the first coating layer is too thin can be avoided.
When the thickness of the second coating layer is in the range of 2-15nm, the surface structure of the second coating layer is stable, and the side reaction with the electrolyte is small, so that the interface side reaction can be effectively lightened, and the high-temperature performance of the secondary battery is improved.
When the thickness of the third coating layer ranges from 2 to 20nm, it is possible to enhance the electrical conductivity properties of the material and improve the compacted density properties of the battery electrode sheet prepared using the positive electrode active material.
In any embodiment, the manganese element content is in the range of 10 wt% to 35 wt%, alternatively in the range of 15 wt% to 30 wt%, more alternatively in the range of 17 wt% to 20 wt%, the phosphorus element content is in the range of 12 wt% to 25 wt%, alternatively in the range of 15 wt% to 20 wt%, and the weight ratio of manganese element to phosphorus element is in the range of 0.90 to 1.25, alternatively 0.95 to 1.20, based on the weight of the positive electrode active material having the core-shell structure.
In the positive electrode active material with the core-shell structure, the content of the manganese element is in the range, so that the problems of poor structural stability, density reduction and the like of the material possibly caused by excessive content of the manganese element can be effectively avoided, and the performances of the secondary battery such as circulation, storage, compaction density and the like are improved; and the problem that the voltage platform is low and the like possibly caused by too small manganese element content can be avoided, so that the energy density of the secondary battery is improved.
In the positive electrode active material with the core-shell structure, the content of the phosphorus element is in the range, so that the following situations can be effectively avoided: if the content of the phosphorus element is too large, the covalent property of P-O is possibly too strong to influence the conduction of small polarons, so that the conductivity of the material is influenced; if the content of the phosphorus element is too small, stability of the lattice structure of the core, pyrophosphate in the first cladding layer, and/or phosphate in the second cladding layer may be lowered, thereby affecting the stability of the whole material.
In the positive electrode active material with the core-shell structure, the weight ratio of the manganese element to the phosphorus element is in the range, so that the following situations can be effectively avoided: if the weight ratio is too large, the dissolution of the transition metal may be increased, affecting the stability of the material and the cycle and storage performance of the secondary battery; if the weight ratio is too small, the discharge voltage plateau of the material may be lowered, and the energy density of the secondary battery may be lowered.
In any embodiment, the positive electrode active material having a core-shell structure has a lattice change rate of 4% or less, optionally 3.8% or less, and more optionally 2.0 to 3.8% before and after complete lithium deintercalation.
The positive electrode active material with the core-shell structure can realize the lattice change rate of less than 4% before and after lithium intercalation. The use of the positive electrode active material can improve the gram capacity and the rate capability of the secondary battery.
In any embodiment, the positive electrode active material having a core-shell structure has a Li/Mn inversion defect concentration of 4% or less, optionally 2.2% or less, and more optionally 1.5 to 2.2%. By the Li/Mn inversion defect concentration being within the above range, mn can be avoided 2+ Barrier Li + And simultaneously improves the gram capacity and the rate capability of the positive electrode active material.
In any practiceIn an embodiment, the positive electrode active material having a core-shell structure has a compacted density of 2.2g/cm at 3T (ton) 3 Above, optionally 2.2g/cm 3 Above and 2.8g/cm 3 The following is given. Thus, increasing the compacted density increases the weight per unit volume of active material, which is more advantageous for increasing the volumetric energy density of the secondary battery.
In any embodiment, the surface oxygen valence state of the positive electrode active material having a core-shell structure is-1.90 or less, alternatively-1.90 to-1.98. Thus, by limiting the surface oxygen valence of the positive electrode active material to the above range, the interfacial side reaction between the positive electrode material and the electrolyte can be reduced, and the cycle of the battery cell, the gas generation performance in high-temperature storage, and the like can be improved.
A second aspect of the present application provides a method for preparing a positive electrode active material, including the steps of:
providing a core material: the chemical formula of the inner core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally one element selected from B, si, N and S;
and (3) coating: respectively provide Li a MP 2 O 7 And/or M b (P 2 O 7 ) c XPO 4 Adding the core material into the suspension, mixing, and sintering to obtain the positive electrode active material, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 6, and the values of a, b and c meet the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c Keeping electric neutrality; each M is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al; x is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;
Wherein the positive electrode active material has a core-shell structure including the core and a shell coating the core, the shell including a first coating layer coating the core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer, the first coating layer including crystalline pyrophosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c The second coating layer comprises crystalline phosphate XPO 4 The third coating layer is carbon.
In any embodiment, the step of providing the core material comprises the steps of:
step (1): mixing and stirring a manganese source, an element A doping agent and acid in a container to obtain manganese salt particles doped with the element A;
step (2): mixing the manganese salt particles doped with the element A with a lithium source, a phosphorus source and a doping agent of the element R in a solvent to obtain slurry, and sintering under the protection of inert gas atmosphere to obtain an inner core doped with the element A and the element R, wherein the inner core doped with the element A and the element R is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S.
In any embodiment, the dopant of the element a is one or more of simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide of one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, respectively.
In any embodiment, the dopant of the element R is one or more of inorganic acid, sub-acid, organic acid, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide of one or more elements selected from B, si, N, and S, respectively;
in any embodiment, said step (1) is performed at a temperature of 20-120 ℃, optionally 40-120 ℃; and/or
The stirring in step (1) is carried out at 400-700rpm for 1-9 hours, optionally 3-7 hours.
When the heating temperature and the stirring time in the preparation process of the core particles are in the ranges, the prepared core and the positive electrode active material prepared from the core have fewer lattice defects, which is beneficial to inhibiting the dissolution of manganese and reducing the interface side reaction of the positive electrode active material and the electrolyte, thereby improving the cycle performance and the safety performance of the secondary battery.
In any embodiment, said step (2) is performed at a temperature of 20-120 ℃, optionally 40-120 ℃, for 1-12h.
In any embodiment, the cladding step comprises:
a first coating step: obtaining a first coating layer suspension by combining a source of element M, a phosphorus source, and an acid and optionally a lithium source; fully mixing the inner core obtained in the inner core step with the first coating layer suspension obtained in the first coating step, drying, and then sintering to obtain a material coated by the first coating layer;
and a second coating step: dissolving a source of element X, a phosphorus source and an acid in a solvent to obtain a second coating layer suspension; fully mixing the material coated by the first coating layer obtained in the first coating step with the second coating layer suspension obtained in the second coating step, drying, and then sintering to obtain a material coated by two coating layers;
and a third coating step: dissolving a carbon source in a solvent, and fully dissolving to obtain a third coating layer solution; and then adding the materials coated by the two coating layers obtained in the second coating step into the third coating layer solution, uniformly mixing, drying, and sintering to obtain the material coated by the three coating layers, namely the positive electrode active material.
In any embodiment, the source of element M is one or more of simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide of one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al, respectively.
In any embodiment, the source of element X is one or more of simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide of one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al, respectively.
In this application, the addition amount of the respective sources of the elements A, R, M, X depends on the target doping amount, and the ratio of the amounts of the lithium source, the manganese source and the phosphorus source accords with the stoichiometric ratio.
In any embodiment, in the first coating step, the pH of the solution in which the source of element M, the source of phosphorus and the acid and optionally the source of lithium are dissolved is controlled to 3.5-6.5, and then stirred and reacted for 1-5 hours, and then the solution is heated to 50-120 ℃ and maintained at that temperature for 2-10 hours, and/or sintering is performed at 650-800 ℃ for 2-6 hours.
By controlling the conditions of the first coating step within the above-described range, it is possible to secure even improvement in the gram capacity of the secondary battery prepared using the positive electrode active material and its cycle and high-temperature storage properties, as well as the gram capacity and rate properties, etc.
In any embodiment, in the second coating step, after the source of element X, the phosphorus source and the acid are dissolved in the solvent, they are stirred and reacted for 1 to 10 hours, and then the solution is heated to 60 to 150 ℃ and maintained at that temperature for 2 to 10 hours, and/or sintering is performed at 500 to 700 ℃ for 6 to 10 hours.
In the step of providing the core material and the first cladding step and the second cladding step, before sintering, that is, in the preparation of the core material in which the chemical reaction occurs (steps (1) - (2)) and in the preparation of the first cladding layer suspension and the second cladding layer suspension, by the reaction temperature and the reaction time selected as described above, the following can be avoided: when the reaction temperature is too low, the reaction cannot occur or the reaction rate is slow; when the temperature is too high, the product is decomposed or forms a heterogeneous phase; when the reaction time is too long, the particle size of the product is larger, and the time and difficulty of the subsequent process can be increased; when the reaction time is too short, the reaction is incomplete, and less product is obtained.
In any embodiment, the sintering in the third coating step is performed at 700-800 ℃ for 6-10 hours.
By controlling the conditions of the third coating step within the above-described range, it is possible to ensure even improvement in the gram capacity and the compacted density of the secondary battery prepared using the positive electrode active material.
The preparation method of the positive electrode active material has the advantages of wide raw material sources, low cost and simple process, and is favorable for realizing industrialization.
A third aspect of the present application provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer comprising the positive electrode active material having a core-shell structure according to the first aspect of the present application or the positive electrode active material prepared by the method according to the second aspect of the present application, and the content of the positive electrode active material in the positive electrode film layer being 90 to 99.5 wt%, preferably 95 to 99.5 wt%, based on the total weight of the positive electrode film layer.
The positive pole piece is used in a battery, and improves the high-temperature cycle performance, the multiplying power performance and the safety performance of the secondary battery.
A fourth aspect of the present application provides a secondary battery comprising the positive electrode tab of the third aspect of the present application. The secondary battery provided by the application has high rate capability, good cycle performance, good safety performance and large battery capacity.
A fifth aspect of the present application provides a battery module comprising the secondary battery according to the fourth aspect of the present application.
A sixth aspect of the present application provides a battery pack comprising the battery module of the fifth aspect of the present application.
A seventh aspect of the present application provides an electric device including at least one of the secondary battery according to the fourth aspect of the present application, the battery module according to the fifth aspect of the present application, or the battery pack according to the sixth aspect of the present application.
The positive electrode plate, the secondary battery, the battery module, the battery pack and the power utilization device comprise the positive electrode active material, so that the positive electrode plate, the secondary battery, the battery module, the battery pack and the power utilization device have higher gram capacity, good cycle performance and safety performance.
Fig. 1 is a schematic view of a positive electrode active material having a core-shell structure as described herein.
Fig. 2 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 3 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 2.
Fig. 4 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 5 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 6 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 5.
Fig. 7 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5 a secondary battery; 51 a housing; 52 electrode assembly; 53 roof assembly
Hereinafter, embodiments of the positive electrode active material, the method for producing the same, the positive electrode sheet, the secondary battery, the battery module, the battery pack, and the electric device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially, or may be performed randomly, or may be performed sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The terms "above", "below" as used in this application include the present number, e.g. "one or more" means one or more, "one or more of" a and B "means" a "," B "or" a and B ".
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
It should be noted that, in this document, the term "coating layer" refers to a material layer coated on the lithium manganese phosphate core, and the material layer may completely or partially coat the lithium manganese phosphate core, and the "coating layer" is used for convenience of description only and is not intended to limit the present invention. Likewise, the term "thickness of the coating layer" refers to the thickness of the material layer coated on the lithium manganese phosphate core in the radial direction of the lithium manganese phosphate core.
The inventor discovers in practical operation that the manganese dissolution of the existing lithium manganese phosphate positive electrode active material is serious in the deep charge and discharge process. Although attempts have been made in the prior art to coat lithium manganese phosphate with lithium iron phosphate to reduce interfacial side reactions, such coating does not prevent the dissolved manganese from continuing to migrate into the electrolyte. The eluted manganese is reduced to metallic manganese after migrating to the negative electrode. The manganese metal thus produced is equivalent to a "catalyst" capable of catalyzing the decomposition of the SEI film (solid electrolyte interphase, solid electrolyte interfacial film) on the surface of the negative electrode, producing by-products; part of the by-product is gas, so that the secondary battery expands to influence the safety performance of the secondary battery; in addition, another portion of the byproduct is deposited on the surface of the negative electrode, which may obstruct the passage of lithium ions into and out of the negative electrode, resulting in an increase in the resistance of the secondary battery, thereby affecting the kinetic performance of the secondary battery. In addition, in order to supplement the lost SEI film, the electrolyte and active lithium inside the battery are continuously consumed, which may have an irreversible effect on the capacity retention rate of the secondary battery.
The inventors have conducted extensive studies and have found that by modifying and multi-layer coating of lithium manganese phosphate, a novel positive electrode active material having a core-shell structure, which can achieve significantly reduced elution of manganese and reduced lattice change rate, can be used in secondary batteries, can improve cycle performance, rate performance, safety performance, and can increase capacity of batteries, can be obtained.
[ Positive electrode active Material ]
The first aspect of the present application provides a novel positive electrode active material having a core-shell structure, which comprises a core and a shell coating the core, wherein the chemical formula of the core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S;
The values of x, y and z satisfy the following condition: keeping the whole kernel electrically neutral;
the shell includes a first cladding layer that coats the inner core, a second cladding layer that coats the first cladding layer, and a third cladding layer that coats the second cladding layer, wherein,
the first coating layer comprises crystalline pyrophosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c Wherein, the method comprises the steps of, wherein,
a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 6, and the values of a, b and c meet the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c The electric neutrality is maintained and the electric power is controlled,
the crystalline pyrophosphates Li a MP 2 O 7 And M b (P 2 O 7 ) c Each M in (2) is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al,
the second coating layer comprises crystalline phosphate XPO 4 Wherein, the method comprises the steps of, wherein,
x is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;
the third coating layer is carbon.
In the chemical formulas of the above cores, unless otherwise specified, when a is two or more elements, the above definition of the y value range is not only a definition of the stoichiometric number of each element as a but also a definition of the sum of the stoichiometric numbers of the respective elements as a. For example, when a is two or more elements A1, A2 … … An, the respective stoichiometric numbers y1, y2 … … yn of A1, A2 … … An each need to fall within the numerical range defined for y in the present application, and the sum of y1, y2 … … yn also needs to fall within the numerical range. Similarly, where R is two or more elements, the definition of the numerical range of the stoichiometry of R in the present application also has the above-described meaning.
In an alternative embodiment, when A is one, two, three or four elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, A y Is Q n1 D n2 E n3 K n4 Wherein n1+n2+n3+n4=y, and n1, n2, n3, n4 are all positive numbers and are not simultaneously zero, Q, D, E, K are each independently one selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally at least one of Q, D, E, K is Fe. Optionally, one of n1, n2, n3, n4 is zero and the others are not zero; more optionally, two of n1, n2, n3, n4 are zero, the remainder being non-zero; still alternatively, three of n1, n2, n3, n4 are zero, the remainder being non-zero. The inner core Li 1+x Mn 1-y A y P 1-z R z O 4 In the manganese site, it is advantageous to dope one, two, three or four of the above-mentioned A elements, optionally one, two or three of the above-mentioned A elements; furthermore, it is advantageous to dope one or both of the R elements in the phosphorus site, which is advantageous in uniformly distributing the doping elements.
The inner core Li 1+x Mn 1-y A y P 1-z R z O 4 The size of x is influenced by the valence state sizes of A and R and the sizes of y and z to ensure that the whole system presents electric neutrality. If the value of x is too small, the lithium content of the whole core system is reduced, and the gram capacity of the material is affected. The value of y limits the total amount of all doping elements, if y is too small, i.e. the doping amount is too small, the doping elements do not work, and if y exceeds 0.5, the Mn content in the system is less, which affects the voltage plateau of the material. The R element is doped at the position of P, and the Z value is limited to be 0.001-0.100 because the P-O tetrahedron is stable and the overlarge Z value can influence the stability of the material.
The positive electrode active material can improve gram capacity, cycle performance and safety performance of the secondary battery. Although the mechanism is not clear, the lithium manganese phosphate positive electrode active material is supposed to be of a core-shell structure, wherein the manganese site and the phosphorus site of the lithium manganese phosphate inner core are respectively doped with the element A and the element R, so that manganese dissolution can be effectively reduced, manganese ions transferred to a negative electrode can be further reduced, electrolyte consumed by SEI film decomposition is reduced, the cycle performance and the safety performance of the secondary battery are improved, mn-O bond adjustment can be promoted, lithium ion migration barrier is reduced, lithium ion migration is promoted, and the rate performance of the secondary battery is improved; the first coating layer comprising crystalline pyrophosphate is coated on the inner core, so that the migration resistance of manganese can be further increased, the dissolution of manganese is reduced, the content of impurity lithium on the surface is reduced, the contact between the inner core and electrolyte is reduced, the side reaction of an interface is reduced, the gas production is reduced, and the high-temperature storage performance, the circulation performance and the safety performance of the secondary battery are improved; by further coating the crystalline phosphate coating layer with excellent lithium ion conducting capacity, the interfacial side reaction on the surface of the positive electrode active material can be effectively reduced, and the high-temperature cycle and storage performance of the secondary battery are improved; by further coating the carbon layer as the third coating layer, the safety performance and the kinetic performance of the secondary battery can be further improved.
In addition, in the inner core, the element A doped at the manganese position of the lithium manganese phosphate is also beneficial to reducing the lattice change rate of the lithium manganese phosphate in the process of deintercalating lithium of the material, improving the structural stability of the lithium manganese phosphate anode material, greatly reducing the dissolution of manganese and reducing the oxygen activity of the particle surface; the element R doped in the phosphorus position is also beneficial to changing the difficulty of Mn-O bond length change, so that the electron conductivity is improved, the lithium ion migration barrier is reduced, the lithium ion migration is promoted, and the rate capability of the secondary battery is improved.
In addition, the whole core system keeps electric neutrality, and defects and impurity phases in the positive electrode active material can be ensured to be as small as possible. If an excessive amount of transition metal (e.g., manganese) is present in the positive electrode active material, since the material system itself is stable in structure, the excessive transition metal is likely to precipitate in the form of simple substance or form a hetero-phase inside the lattice, and maintaining electrical neutrality can make such a hetero-phase as small as possible. In addition, the neutrality of the system is ensured, and lithium vacancies can be generated in the material under partial conditions, so that the dynamics performance of the material is more excellent.
The average particle size of the core prepared by the method is 50-500nm, and the Dv50 is 200-300nm. The primary particle size of the core is in the range of 50-500nm, and Dv50 is 200-300nm. If the average particle diameter of the core is too large (more than 500 nm), the gram capacity exertion of the secondary battery using the material may be affected; if the average particle diameter of the inner core is too small, the specific surface area is large, agglomeration is easy, and uniform coating is difficult to realize.
In the present application, the median particle diameter Dv50 refers to a particle diameter corresponding to a cumulative volume distribution percentage of the material of 50%. In this application, the median particle diameter Dv50 of a material can be determined using laser diffraction particle size analysis. For example, reference standard GB/T19077-2016, using a laser particle size analyzer (e.g., malvern Master Size 3000).
By process control (e.g., thorough mixing, grinding of the materials from various sources), uniform distribution of the elements in the lattice can be ensured without agglomeration. Main characteristic peak position in XRD pattern of lithium manganese phosphate doped with A element and R element and undoped LiMnPO 4 It is stated that the doping process does not introduce impurity phases and therefore the improvement in core performance is mainly due to elemental doping and not impurity phases. After the present inventors prepared the positive electrode active material, the intermediate region of the prepared positive electrode active material particles was cut by a focused ion beam (abbreviated as FIB), and the test was performed by a transmission electron microscope (abbreviated as TEM) and X-ray spectroscopy (abbreviated as EDS), which revealed that the elements were uniformly distributed and did not appear aggregation.
In this application crystalline state means a crystallinity of 50% or more, i.e. 50% -100%. A crystallinity of less than 50% is referred to as glassy. Crystalline pyrophosphates and crystalline phosphates as described herein have a crystallinity of 50% to 100%. The pyrophosphate and the phosphate with certain crystallinity are beneficial to fully playing the functions of preventing manganese from dissolving out and leading lithium ions of the phosphate coating and reducing interface side reactions of the pyrophosphate coating, and can better perform lattice matching, so that the coating can be more tightly combined.
In the present application, the crystallinity of the crystalline pyrophosphate of the first coating substance and the crystalline phosphate of the second coating substance of the positive electrode active material may be measured by conventional technical means in the art, for example, by a density method, an infrared spectroscopy method, a differential scanning calorimetry method, and a nuclear magnetic resonance absorption method, and may also be measured by, for example, an X-ray diffraction method.
The method for testing the crystallinity of the crystalline pyrophosphate of the first coating layer and the crystalline phosphate of the second coating layer of the positive electrode active material by using a specific X-ray diffraction method can comprise the following steps:
taking a certain amount of positive electrode active material powder, measuring the total scattering intensity by X-rays, wherein the total scattering intensity is the sum of the scattering intensities of the whole space substances, and is only related to the intensity of primary rays, the chemical structure of the positive electrode active material powder and the total number of electrons participating in diffraction, namely the mass, and is not related to the sequence state of a sample; the crystalline and amorphous scatterings are then separated from the diffractogram, and the crystallinity is the ratio of the crystalline fraction scatter to the total scattered intensity.
In the present application, the crystallinity of pyrophosphate and phosphate in the coating layer can be adjusted by adjusting the process conditions of the sintering process, such as the sintering temperature, the sintering time, and the like.
In the application, because metal ions are difficult to migrate in the pyrophosphate, the pyrophosphate can effectively isolate doped metal ions from the electrolyte as the first coating layer. The crystalline pyrophosphate has stable structure, so that the crystalline pyrophosphate coating can effectively inhibit the dissolution of transition metal and improve the cycle performance.
The bond between the first cladding layer and the core is similar to a heterojunction, the degree of firmness of which is limited by the degree of lattice matching. When the lattice mismatch is less than 5%, the lattice match is better, and the lattice mismatch and the lattice match are easy to combine tightly. The tight combination can ensure that the coating layer cannot fall off in the subsequent circulation process, thereby being beneficial to ensuring the long-term stability of the material. The degree of bonding between the first cladding layer and the core is measured primarily by calculating the degree of mismatch of the lattice constants of the core and the cladding. In the application, after the elements A and R are doped in the inner core, the matching degree between the inner core and the first coating layer is improved compared with that between the inner core and the first coating layer, and the inner core and the pyrophosphate coating layer can be more tightly combined together.
Crystalline phosphate is chosen as the second coating layer, first, because it has a high degree of lattice match (3% mismatch) with the crystalline pyrophosphate of the first coating layer; secondly, the stability of the phosphate is better than that of the pyrophosphate, and coating the pyrophosphate with the phosphate is beneficial to improving the stability of the material. The crystalline phosphate has a stable structure and excellent lithium ion conducting capacity, so that the coating of the crystalline phosphate can effectively reduce the interfacial side reaction on the surface of the positive electrode active material, thereby improving the high-temperature cycle and storage performance of the secondary battery. The lattice matching method between the second cladding layer and the first cladding layer is similar to the bonding between the first cladding layer and the core, and when the lattice mismatch is 5% or less, the lattice matching is good, and the two are easily bonded tightly.
The main reason for the carbon coating as the third layer is that the electron conductivity of the carbon layer is good. Since an electrochemical reaction occurs when applied in a secondary battery, participation of electrons is required, and thus, in order to increase electron transport between particles and electron transport at different positions on the particles, carbon having excellent conductive properties may be used to coat the positive electrode active material. The carbon coating can effectively improve the conductivity and desolvation ability of the positive electrode active material.
Fig. 1 is a schematic view of a positive electrode active material of an ideal three-layer coating structure. As shown, the innermost circle schematically represents the core, with the first cladding layer, the second cladding layer, and the third cladding layer being in that order from the inside to the outside. The figure shows the ideal state that each layer is completely coated, and in practice, each layer of coating can be completely coated or partially coated.
In some embodiments, the primary particles of the positive electrode active material have an average particle diameter ranging from 50 to 500nm and a volume median particle diameter Dv50 ranging from 200 to 300 nm. Since the particles agglomerate, the secondary particle size after agglomeration may be 500-40000nm as measured in practice. The size of the positive electrode active material particles can affect the processing of the material and the compacted density performance of the pole piece. By selecting the average particle diameter of the primary particles within the above range, the following can be avoided: the primary particles of the positive electrode active material have an average particle size which is too small, may cause particle agglomeration, are difficult to disperse, and require more binder, resulting in poor brittleness of the electrode sheet; the primary particles of the positive electrode active material have too large an average particle diameter, and may have large inter-particle voids and reduced compacted density.
Through the scheme, the lattice change rate and Mn dissolution of the lithium manganese phosphate in the lithium deintercalation process can be effectively inhibited, so that the high-temperature cycle stability and the high-temperature storage performance of the secondary battery are improved.
In some embodiments, the crystalline pyrophosphate in the first cladding layer has an interplanar spacing in the range of 0.293-0.470nm and an included angle in the crystal direction (111) in the range of 18.00 ° -32.00 °; the crystal-state phosphate in the second coating layer has a interplanar spacing range of 0.244-0.425nm and an included angle of the crystal direction (111) of 20.00-37.00 degrees.
The first coating layer and the second coating layer in the positive electrode active material described in the application use crystalline substances. The crystalline pyrophosphates and crystalline phosphates in the coating may be characterized by means conventional in the art, and may also be characterized, for example, by means of Transmission Electron Microscopy (TEM). Under TEM, the core and cladding layers can be distinguished by testing the interplanar spacing.
The specific test method for the interplanar spacing and included angle of crystalline pyrophosphates and crystalline phosphates in the coating layer can comprise the following steps:
taking a certain amount of coated positive electrode active material sample powder in a test tube, injecting a solvent such as alcohol into the test tube, then fully stirring and dispersing, then dripping a proper amount of the solution on a 300-mesh copper mesh by using a clean disposable plastic suction tube, at the moment, part of the powder is remained on the copper mesh, and transferring the copper mesh together with a sample into a TEM sample cavity for testing, so as to obtain a TEM test original picture, and storing the original picture.
And opening the original picture obtained by the TEM test in diffractometer software, carrying out Fourier transform to obtain a diffraction pattern, measuring the distance from a diffraction spot to the central position in the diffraction pattern, and calculating the included angle according to a Bragg equation to obtain the interplanar spacing.
The difference between the range of the interplanar spacing of the crystalline pyrophosphate and the existence of the crystalline phosphate can be directly judged by the numerical value of the interplanar spacing.
The crystalline pyrophosphates and crystalline phosphates within the ranges of the interplanar spacing and the included angles can more effectively inhibit the lattice change rate and Mn dissolution of the lithium manganese phosphate in the lithium deintercalation process, thereby improving the high-temperature cycle performance, the cycle stability and the high-temperature storage performance of the secondary battery.
In some embodiments, in the core, the ratio of y to 1-y is 1:10 to 1:1, alternatively 1:4 to 1:1. where y represents the sum of the stoichiometric numbers of Mn-site doping element A. When the above conditions are satisfied, the energy density and cycle performance of the secondary battery using the positive electrode active material may be further improved.
In some embodiments, in the core, the ratio of z to 1-z is 1:9 to 1:999, alternatively 1:499 to 1:249. where z represents the sum of the stoichiometries of the P-site doping elements R. When the above conditions are satisfied, the energy density and cycle performance of the secondary battery using the positive electrode active material may be further improved.
In some embodiments, the carbon of the third coating layer is a mixture of SP2 morphology carbon and SP3 morphology carbon, optionally, the molar ratio of SP2 morphology carbon to SP3 morphology carbon is any value in the range of 0.1-10, optionally, any value in the range of 2.0-3.0.
In some embodiments, the molar ratio of SP2 morphology carbon to SP3 morphology carbon may be about 0.1, about 0.2, about 03, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10, or within any range of any of the above.
In the present application, a value of "about" means a range, and means a range of ±10% of the value.
By selecting the morphology of carbon in the carbon coating layer, the overall electrical performance of the secondary battery is improved. Specifically, by using a mixed form of SP 2-form carbon and SP 3-form carbon and limiting the ratio of SP 2-form carbon to SP 3-form carbon to a certain range, the following can be avoided: if the carbon in the coating layer is in amorphous SP3 form, the conductivity is poor; in the case of the graphitized SP2 form, although the conductivity is good, the lithium ion channels are small, which is disadvantageous for the deintercalation of lithium. In addition, the molar ratio of SP 2-form carbon to SP 3-form carbon is limited to the above range, and thus, not only can good conductivity be achieved, but also a passage of lithium ions can be ensured, thereby facilitating realization of the function of the secondary battery and its cycle performance.
The mixing ratio of the SP2 morphology and the SP3 morphology of the third coated carbon may be controlled by the sintering conditions such as the sintering temperature and the sintering time. For example, in the case of preparing the third coating layer using sucrose as a carbon source, after cracking sucrose at a high temperature, the carbon coating layer having both SP3 and SP2 morphology is produced by depositing on the second coating layer while being subjected to a high temperature. The ratio of SP2 morphology carbon to SP3 morphology carbon can be controlled by selecting pyrolysis conditions and sintering conditions.
The structure and characteristics of the third coated carbon can be determined by Raman (Raman) spectroscopy, and the specific test method is as follows: the molar ratio of Id/Ig (where Id is the peak intensity of the SP3 form carbon and Ig is the peak intensity of the SP2 form carbon) was confirmed by peak-splitting the spectra of the Raman test.
In some embodiments, the first cladding layer is present in an amount greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core; and/or
The second cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, more alternatively from 2 to 4 wt%, based on the weight of the core; and/or
The third cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, and more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core.
In this application, the coating amount of each layer is not zero.
In the positive electrode active material with the core-shell structure, the cladding amount of the three-layer cladding layer is preferably within the above range, so that the inner core can be fully clad, and meanwhile, the dynamic performance and the safety performance of the secondary battery are further improved on the premise of not sacrificing the gram capacity of the positive electrode active material.
With respect to the first coating layer, by the coating amount falling within the above range, the following can be avoided: too little coating means that the coating layer is thinner and migration of transition metal may not be effectively hindered; an excessive coating amount means that the coating layer is too thick and affects Li + And further affects the rate capability of the material.
With respect to the second coating layer, by the coating amount falling within the above range, the following can be avoided: excessive coating can affect the overall plateau voltage of the material; too little coating amount may not achieve a sufficient coating effect.
For the third coating layer, carbon coating mainly plays a role in enhancing electron transport between particles, however, since a large amount of amorphous carbon is also contained in the structure, the density of carbon is low, and thus if the coating amount is too large, the compacted density of the pole piece is affected.
In some embodiments, the first cladding layer has a thickness of 1-10nm; and/or
The thickness of the second coating layer is 2-15nm; and/or
The thickness of the third coating layer is 2-25nm.
In some embodiments, the thickness of the first cladding layer may be about 2nm, about 3nm, about 4nm, about 5nm, about 6nm, about 7nm, about 8nm, about 9nm, or about 10nm, or within any range of any of the values recited above.
In some embodiments, the thickness of the second cladding layer may be about 2nm, about 3nm, about 4nm, about 5nm, about 6nm, about 7nm, about 8nm, about 9nm, about 10nm, about 11nm, about 12nm, about 13nm, about 14nm, about 15nm, or within any range of any of the values recited above.
In some embodiments, the thickness of the third layer of cladding may be about 2nm, about 3nm, about 4nm, about 5nm, about 6nm, about 7nm, about 8nm, about 9nm, about 10nm, about 11nm, about 12nm, about 13nm, about 14nm, about 15nm, about 16nm, about 17nm, about 18nm, about 19nm, about 20nm, about 21nm, about 22nm, about 23nm, about 24nm, or about 25nm, or within any range of any of the values recited above.
When the thickness of the first coating layer is in the range of 1-10nm, adverse effects on the dynamic properties of the material that may occur when too thick can be avoided, and the problem that migration of transition metal ions may not be effectively hindered when too thin can be avoided.
When the thickness of the second coating layer is in the range of 2-15nm, the surface structure of the second coating layer is stable, and the side reaction with the electrolyte is small, so that the interface side reaction can be effectively lightened, and the high-temperature performance of the secondary battery is improved.
When the thickness of the third coating layer ranges from 2 to 25nm, it is possible to enhance the electrical conductivity of the material and improve the compaction performance of the battery electrode sheet prepared using the positive electrode active material.
The thickness test of the coating layer is mainly carried out by FIB, and the specific method can comprise the following steps: and randomly selecting single particles from the positive electrode active material powder to be detected, cutting a sheet with the thickness of about 100nm from the middle position or the vicinity of the middle position of the selected particles, then carrying out TEM test on the sheet, measuring the thickness of a coating layer, measuring 3-5 positions, and taking an average value.
In some embodiments, the manganese element content is in the range of 10 wt% to 35 wt%, alternatively in the range of 15 wt% to 30 wt%, more alternatively in the range of 17 wt% to 20 wt%, the phosphorus element content is in the range of 12 wt% to 25 wt%, alternatively in the range of 15 wt% to 20 wt%, and the weight ratio of manganese element to phosphorus element is in the range of 0.90 to 1.25, alternatively 0.95 to 1.20, based on the weight of the positive electrode active material.
In the present application, in the case where manganese is contained in only the core of the positive electrode active material, the content of manganese may correspond to the content of the core.
In the application, the content of the manganese element is limited in the range, so that the problems of poor structural stability, low density and the like of the material possibly caused by excessive content of the manganese element can be effectively avoided, and the performances of the secondary battery such as circulation, storage, compaction and the like are improved; and the problem that the voltage platform is low and the like possibly caused by too small manganese element content can be avoided, so that the energy density of the secondary battery is improved.
In the application, the content of the phosphorus element is limited to be within the above range, so that the following situations can be effectively avoided: if the content of the phosphorus element is too large, the covalent property of P-O is possibly too strong to influence the conduction of small polarons, so that the conductivity of the material is influenced; if the phosphorus content is too small, the stability of the lattice structure of the core, pyrophosphate in the first cladding layer, and/or phosphate in the second cladding layer may be reduced, thereby affecting the stability of the material as a whole.
The weight ratio of manganese to phosphorus content has the following effect on the performance of the secondary battery: the excessive weight ratio means that excessive manganese element is dissolved out, so that the stability and gram capacity exertion of the positive electrode active material are affected, and the cycle performance and storage performance of the secondary battery are further affected; when the weight ratio is too small, it means that too much phosphorus element tends to form a hetero phase, and the discharge voltage plateau of the material is lowered, so that the energy density of the secondary battery is lowered.
The measurement of manganese and phosphorus can be performed using techniques conventional in the art. In particular, the contents of manganese and phosphorus were determined by the following method: dissolving the material in dilute hydrochloric acid (the concentration is 10-30%), testing the content of each element of the solution by utilizing ICP, and then measuring and converting the content of manganese element to obtain the weight ratio of the manganese element.
In some embodiments, the positive electrode active material having a core-shell structure has a lattice change rate of 4% or less, optionally 3.8% or less, and more optionally 2.0 to 3.8% before and after complete lithium deintercalation.
Lithium manganese phosphate (LiMnPO) 4 ) Is a two-phase reaction. The interfacial stress of two phases is determined by the size of the lattice change rate before and after lithium intercalation, and the smaller the lattice change rate is, the smaller the interfacial stress is, li + The easier the transmission. Therefore, reducing the rate of lattice change of the core will be beneficial to enhancing Li + Thereby improving the rate capability of the secondary battery. The positive electrode active material with the core-shell structure can realize the lattice change rate of less than 4% before and after lithium intercalation, so that the rate capability of the secondary battery can be improved by using the positive electrode active material. The rate of lattice change can be measured by methods known in the art, such as X-ray diffraction pattern (XRD).
In some embodiments, the positive electrode active material having a core-shell structure has a Li/Mn inversion defect concentration of 4% or less, alternatively 2.2% or less, and more alternatively 1.5 to 2.2%.
The Li/Mn inversion defect refers to LiMnPO 4 In the crystal lattice, li + With Mn 2+ Is interchanged. Correspondingly, the Li/Mn inversion defect concentration refers to the concentration corresponding to Mn 2+ Li exchanged + Occupying Li + Percent of the total amount. In this application, the Li/Mn inversion defect concentration can be measured, for example, in accordance with JIS K0131-1996.
The positive electrode active material with the core-shell structure can realize the low Li/Mn inversion defect concentration. Although the mechanism is not yet clear, the inventors speculated that due to LiMnPO 4 In the crystal lattice, li + With Mn 2+ Can be interchanged in position, and Li + The transmission channel is a one-dimensional channel, thus Mn 2+ In Li + Will be difficult to migrate in the channel, thereby impeding Li + Is transmitted by (a) to. Thus, the positive electrode active material having a core-shell structure described in the present application can avoid Mn because the concentration of Li/Mn inversion defects is low within the above range 2+ Barrier Li + And simultaneously improves gram capacity exertion and rate capability of the positive electrode active material.
In some embodiments, the positive electrode active material has a compacted density of 2.2g/cm at 3T 3 Above, optionally 2.2g/cm 3 Above and 2.8g/cm 3 The following is given. The higher the compacted density, the greater the weight per unit volume of active material, and thus increasing the compacted density is beneficial for increasing the volumetric energy density of the cell. The compaction density may be measured according to GB/T24533-2009.
In some embodiments, the surface oxygen valence state of the positive electrode active material is-1.90 or less, alternatively-1.90 to-1.98.
The stable valence state of oxygen is-2, the closer the valence state is to-2, the stronger the electron-obtaining capability, namely the stronger the oxidizing property, and the surface valence state is below-1.7 in general. The surface oxygen valence state of the positive electrode active material is limited in the range, so that the interface side reaction of the positive electrode material and the electrolyte can be reduced, and the performances of circulation, high-temperature storage, gas production and the like of the battery cell are improved.
The surface oxygen valence state can be measured by methods known in the art, for example, by Electron Energy Loss Spectroscopy (EELS).
A second aspect of the present application provides a method for preparing a positive electrode active material, including the steps of:
providing a core material: the chemical formula of the inner core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, and A is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and MgA seed element, wherein R is one or more elements selected from B, si, N and S, optionally, R is one element selected from B, si, N and S;
and (3) coating: respectively provide Li a MP 2 O 7 And/or M b (P 2 O 7 ) c XPO 4 Adding the core material into the suspension, mixing, and sintering to obtain the positive electrode active material, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 6, and the values of a, b and c meet the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c Keeping electric neutrality; each M is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al; x is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;
wherein the positive electrode active material has a core-shell structure including the core and a shell coating the core, the shell including a first coating layer coating the core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer, the first coating layer including crystalline pyrophosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c The second coating layer comprises crystalline phosphate XPO 4 The third coating layer is carbon.
In some embodiments, the step of providing the core material comprises the steps of:
step (1): mixing and stirring a manganese source, an element A doping agent and acid in a container to obtain manganese salt particles doped with the element A;
step (2): mixing the manganese salt particles doped with the element A with a lithium source, a phosphorus source and a doping agent of the element R in a solvent to obtain slurry, and sintering under the protection of inert gas atmosphere to obtain the inner doped with the element A and the element RA core, wherein the core doped with the element A and the element R is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S.
The source of the material in the preparation method of the present application is not particularly limited, and the source of a certain element may include one or more of simple substance, sulfate, halide, nitrate, organic acid salt, oxide or hydroxide of the element, and the precursor is a source that can achieve the purpose of the preparation method of the present application.
In some embodiments, the dopant of element a is one or more of the elements selected from the group consisting of simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide, respectively, of Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge.
In some embodiments, the dopant of element R is one or more of an inorganic acid, an organic acid, a sulfate, a chloride, a nitrate, an organic acid salt, an oxide, a hydroxide of each of one or more elements selected from B, si, N, and S;
in this application, the manganese source may be a manganese-containing material known in the art that may be used to prepare lithium manganese phosphate. As an example, the manganese source may be one or more selected from elemental manganese, manganese dioxide, manganese phosphate, manganese oxalate, manganese carbonate.
In this application, the acid may be one or more selected from the group consisting of organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, silicic acid, sub-silicic acid, and the like, and organic acids such as oxalic acid. In some embodiments, the acid is a dilute organic acid at a concentration of 60 wt.% or less.
In this application, the lithium source may be a lithium-containing material known in the art that can be used to prepare lithium manganese phosphate. As an example, the lithium source is one or more selected from lithium carbonate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate.
In this application, the phosphorus source may be a phosphorus-containing material known in the art as useful for preparing lithium manganese phosphate. As an example, the phosphorus source is one or more selected from the group consisting of diammonium phosphate, monoammonium phosphate, ammonium phosphate, and phosphoric acid.
In some alternative embodiments, after the manganese source, the dopant of element a, and the acid are reacted in a solvent to obtain a manganese salt suspension doped with element a, the suspension is filtered, dried, and sanded to obtain element a doped manganese salt particles having a particle size of 50-200 nm.
In some alternative embodiments, the slurry in step (2) is dried to obtain a powder, and the powder is sintered to obtain a core doped with element a and element R.
In some embodiments, the step (1) is performed at a temperature of 20-120 ℃, optionally 40-120 ℃; and/or
The stirring in step (1) is carried out at 400-700rpm for 1-9 hours, optionally 3-7 hours.
Alternatively, the reaction temperature in step (1) may be conducted at about 30 ℃, about 50 ℃, about 60 ℃, about 70 ℃, about 80 ℃, about 90 ℃, about 100 ℃, about 110 ℃, or about 120 ℃; the stirring in step (1) is performed for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, or about 9 hours; alternatively, the reaction temperature and stirring time in the step (1) may be within any range of any of the above values.
In some embodiments, the step (2) is performed at a temperature of 20-120 ℃, optionally 40-120 ℃, for 1-12 hours. Alternatively, the reaction temperature in step (2) may be conducted at about 30 ℃, about 50 ℃, about 60 ℃, about 70 ℃, about 80 ℃, about 90 ℃, about 100 ℃, about 110 ℃, or about 120 ℃; the mixing in step (2) is performed for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, or about 12 hours; alternatively, the reaction temperature and mixing time in step (2) may be within any range of any of the values described above.
When the temperature and time in the preparation process of the core particles are in the ranges, the prepared core and the positive electrode active material prepared from the core have fewer lattice defects, which is beneficial to inhibiting the dissolution of manganese and reducing the interface side reaction of the positive electrode active material and electrolyte, thereby improving the cycle performance and the safety performance of the secondary battery.
In some embodiments, optionally, during the preparation of the element a and element R doped dilute manganese acid particles, the solution pH is controlled to be 3.5-6, optionally, the solution pH is controlled to be 4-6, and more optionally, the solution pH is controlled to be 4-5. In this application, the pH of the resulting mixture may be adjusted by methods commonly used in the art, for example, by adding an acid or a base.
In some embodiments, optionally, in step (2), the molar ratio of the manganese salt particles to the lithium source, phosphorus source is 1:0.5-2.1:0.5-2.1, more optionally, the molar ratio of the manganese salt particles doped with element a to the lithium source, phosphorus source is about 1:1:1.
in some embodiments, optionally, the sintering conditions during the preparation of the a-element and R-element doped lithium manganese phosphate are: sintering for 4-10 hours at 600-950 ℃ under inert gas or mixed atmosphere of inert gas and hydrogen; alternatively, the sintering may be performed at about 650 ℃, about 700 ℃, about 750 ℃, about 800 ℃, about 850 ℃, or about 900 ℃ for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours; alternatively, the sintering temperature and sintering time may be within any range of any of the values described above. In the process of preparing the manganese lithium phosphate doped with the element A and the element R, the lower crystallinity of the material core can be caused when the sintering temperature is too low and the sintering time is too short, the whole performance exertion can be influenced, and when the sintering temperature is too high, the impurity phase is easy to appear in the material core, so that the whole performance exertion is influenced; when the sintering time is too long, the core particle length of the material is larger, so that gram capacity exertion, compaction density, multiplying power performance and the like are influenced.
In some alternative embodiments, the protective atmosphere is optionally a mixture of 70-90% by volume nitrogen and 10-30% by volume hydrogen.
In some embodiments, the coating step comprises:
a first coating step: dissolving a source of element M, a phosphorus source, an acid and optionally a lithium source in a solvent to obtain a first coating layer suspension; fully mixing the inner core obtained in the inner core step with the first coating layer suspension obtained in the first coating step, drying, and then sintering to obtain a material coated by the first coating layer;
and a second coating step: dissolving a source of element X, a phosphorus source and an acid in a solvent to obtain a second coating layer suspension; fully mixing the material coated by the first coating layer obtained in the first coating step with the second coating layer suspension obtained in the second coating step, drying, and then sintering to obtain a material coated by two coating layers;
and a third coating step: dissolving a carbon source in a solvent, and fully dissolving to obtain a third coating layer solution; and then adding the materials coated by the two coating layers obtained in the second coating step into the third coating layer solution, uniformly mixing, drying, and sintering to obtain the material coated by the three coating layers, namely the positive electrode active material.
In some embodiments, the source of element M is one or more of the elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al, respectively, simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide.
In some embodiments, the source of element X is one or more of the elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al, respectively, simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide, hydroxide.
The addition amount of the respective sources of the elements A, R, M, X depends on the target doping amount, and the ratio of the amounts of the lithium source, the manganese source and the phosphorus source corresponds to the stoichiometric ratio.
As an example, the carbon source is one or more selected from starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, citric acid.
In some embodiments, in the first coating step, the pH of the solution in which the source of element M, the source of phosphorus and the acid and optionally the source of lithium are dissolved is controlled to 3.5-6.5, then stirred and reacted for 1-5 hours, then the solution is warmed to 50-120 ℃ and maintained at that temperature for 2-10 hours, and/or sintering is performed at 650-800 ℃ for 2-6 hours.
Optionally, in the first coating step, the reaction is fully performed. Alternatively, in the first coating step, the reaction is conducted for about 1.5 hours, about 2 hours, about 3 hours, about 4 hours, about 4.5 hours, or about 5 hours. Alternatively, in the first coating step, the reaction time of the reaction may be within any of the ranges of any of the values described above.
Optionally, in the first coating step, the pH of the solution is controlled to be 4-6. Optionally, in the first coating step, the solution is warmed to about 55 ℃, about 60 ℃, about 70 ℃, about 80 ℃, about 90 ℃, about 100 ℃, about 110 ℃, or about 120 ℃ and held at that temperature for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours; alternatively, in the first cladding step, the elevated temperature and the holding time may be within any range of any of the values described above.
Alternatively, in the first cladding step, the sintering may be at about 650 ℃, about 700 ℃, about 750 ℃, or about 800 ℃ for about 2 hours, about 3 hours, about 4 hours, about 5 hours, or about 6 hours; alternatively, the sintering temperature and sintering time may be within any range of any of the values described above.
In the first cladding step, by controlling the sintering temperature and time within the above ranges, the following can be avoided: when the sintering temperature in the first cladding step is too low and the sintering time is too short, the crystallinity of the first cladding layer is caused to be low,the amorphous material is more, which may cause a decrease in the effect of inhibiting the dissolution of metal, thereby affecting the cycle performance and high-temperature storage performance of the secondary battery; when the sintering temperature is too high, the first coating layer is in a mixed phase, and the effect of inhibiting metal dissolution is also affected, so that the circulation, the high-temperature storage performance and the like of the secondary battery are affected; if the sintering time is too long, the thickness of the first coating layer will be increased, affecting Li + Thereby affecting gram capacity performance, rate performance, and the like of the material.
In some embodiments, the second coating step, after dissolving the source of element X, the phosphorus source and the acid in a solvent, is stirred and reacted for 1-10 hours, then the solution is warmed to 60-150 ℃ and maintained at that temperature for 2-10 hours, and/or sintering is performed at 500-700 ℃ for 6-10 hours.
Optionally, in the second coating step, the reaction proceeds substantially. Alternatively, in the second coating step, the reaction is conducted for about 1.5 hours, about 2 hours, about 3 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours. Alternatively, in the second coating step, the reaction time of the reaction may be within any of the ranges of any of the values described above.
Optionally, in the second coating step, the solution is warmed to about 65 ℃, about 70 ℃, about 80 ℃, about 90 ℃, about 100 ℃, about 110 ℃, about 120 ℃, about 130 ℃, about 140 ℃ or about 150 ℃ and held at that temperature for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours; alternatively, in the second coating step, the elevated temperature and the holding time may be within any range of any of the values described above.
In the step of providing the core material and the first cladding step and the second cladding step, before sintering, that is, in the preparation of the core material in which the chemical reaction occurs (steps (1) - (2)) and in the preparation of the first cladding layer suspension and the second cladding layer suspension, by selecting appropriate reaction temperature and reaction time as described above, the following can be avoided: when the reaction temperature is too low, the reaction cannot occur or the reaction rate is slow; when the temperature is too high, the product is decomposed or forms a heterogeneous phase; when the reaction time is too long, the particle size of the product is larger, and the time and difficulty of the subsequent process can be increased; when the reaction time is too short, the reaction is incomplete, and less product is obtained.
Alternatively, in the second coating step, the sintering may be at about 550 ℃, about 600 ℃, or about 700 ℃ for about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours; alternatively, the sintering temperature and sintering time may be within any range of any of the values described above.
In the second coating step, by controlling the sintering temperature and time within the above ranges, the following can be avoided: when the sintering temperature in the second coating step is too low and the sintering time is too short, the crystallinity of the second coating layer is low, the amorphous state is more, and the performance of reducing the surface reactivity of the material is reduced, so that the cycle, the high-temperature storage performance and the like of the secondary battery are influenced; when the sintering temperature is too high, the second coating layer is in a mixed phase, and the effect of reducing the surface reactivity of the material is also affected, so that the circulation and high-temperature storage performance of the secondary battery are affected; when the sintering time is too long, the thickness of the second coating layer is increased, the voltage platform of the material is affected, the energy density of the material is reduced, and the like.
In some embodiments, the sintering in the third coating step is performed at 700-800 ℃ for 6-10 hours. Optionally, in the third coating step, the sintering may be at about 700 ℃, about 750 ℃, or about 800 ℃ for about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours; alternatively, the sintering temperature and sintering time may be within any range of any of the values described above.
In the third coating step, by controlling the sintering temperature and time within the above ranges, the following can be avoided: when the sintering temperature in the third coating step is too low, the graphitization degree of the third coating layer is reduced, the conductivity of the third coating layer is influenced, and the gram capacity of the material is influenced; when the sintering temperature is too high, the third coating layer is causedToo high graphitization degree, affecting Li + Thereby affecting gram capacity exertion of the material, etc.; when the sintering time is too short, the coating layer is too thin, so that the conductivity of the coating layer is influenced, and the gram capacity of the material is influenced; if the sintering time is too long, the coating layer is too thick, which affects the compaction density of the material.
In the first coating step, the second coating step and the third coating step, the drying is performed at a drying temperature of 100 ℃ to 200 ℃, optionally 110 ℃ to 190 ℃, more optionally 120 ℃ to 180 ℃, even more optionally 120 ℃ to 170 ℃, most optionally 120 ℃ to 160 ℃, and the drying time is 3 to 9 hours, optionally 4 to 8 hours, more optionally 5 to 7 hours, most optionally about 6 hours.
The anode active material prepared by the preparation method of the anode active material reduces the elution quantity of Mn and Mn doped elements after circulation of the secondary battery, and improves the high-temperature stability, the high-temperature circulation performance and the rate performance. In addition, the raw materials are wide in source, low in cost and simple in process, and industrialization is facilitated.
[ Positive electrode sheet ]
A third aspect of the present application provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer comprising the positive electrode active material having a core-shell structure according to the first aspect of the present application or the positive electrode active material prepared by the method according to the second aspect of the present application, and the content of the positive electrode active material in the positive electrode film layer is 10 wt% or more, optionally 90 to 99.5 wt%, more optionally 95 to 99.5 wt%, based on the total weight of the positive electrode film layer.
In this application, as an example, the positive electrode current collector has two surfaces opposing in the thickness direction thereof, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In the present application, the positive electrode active material described in the present application is used.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the binder is present in the positive electrode sheet in an amount of 0.4 to 5.5 wt%, alternatively 0.4 to 4.5 wt%, the conductive agent is present in an amount of 0.1 to 2.5 wt%, alternatively 0.1 to 0.5 wt%, and the other additives are present in an amount of 0.001 to 1 wt%, based on the total weight of the positive electrode sheet.
In some embodiments, the coating weight of the positive electrode sheet is 0.28-0.45g/1540.25mm 2 The compaction density reaches 2.0g/cm 3 The above can be 2.2-2.8g/cm 3 。
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a secondary battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloy. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent may be at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The type of electrolyte is not particularly limited in this application, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be at least one selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethylsulfone, methylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
Secondary battery
A fourth aspect of the present application provides a secondary battery comprising the positive electrode active material having a core-shell structure described in the first aspect of the present application or the positive electrode active material prepared by the method described in the second aspect of the present application or the positive electrode tab described in the third aspect of the present application.
The secondary battery comprises a positive electrode plate, a negative electrode plate, an electrolyte and a separation film. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
In some embodiments, the lithium ion secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the lithium ion secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The outer package of the lithium ion secondary battery may also be a pouch type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
Hereinafter, the secondary battery, the battery module, the battery pack, and the electric device of the present application will be described with appropriate reference to the accompanying drawings.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 2 is a secondary battery 5 of a square structure as one example.
In some embodiments, referring to fig. 3, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
In some embodiments, the lithium ion secondary battery may be assembled into a battery module, and the number of lithium ion batteries contained in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Accordingly, a fifth aspect of the present application provides a battery module comprising the secondary battery according to the fourth aspect of the present application.
Fig. 4 is a battery module 4 as an example. Referring to fig. 4, in the battery module 4, a plurality of lithium ion batteries 5 may be arranged in order along the length direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of lithium ion batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a housing having an accommodating space in which the plurality of lithium ion batteries 5 are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Accordingly, a sixth aspect of the present application provides a battery pack comprising a battery module according to the fifth aspect of the present application.
Fig. 5 and 6 are battery packs 1 as an example. Referring to fig. 5 and 6, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
A seventh aspect of the present application provides an electric device comprising at least one of the secondary battery according to the fourth aspect of the present application, the battery module according to the fifth aspect of the present application, or the battery pack according to the sixth aspect of the present application. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 7 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
The positive electrode plate, the secondary battery, the battery module, the battery pack and the power utilization device comprise the positive electrode active material, so that the positive electrode plate, the secondary battery, the battery module, the battery pack and the power utilization device have higher gram capacity, good cycle performance and safety performance.
Examples
Hereinafter, embodiments of the present application are described. The embodiments described below are exemplary only for the purpose of illustrating the present application and are not to be construed as limiting the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The contents of the respective components in the examples of the present invention are based on the mass containing no crystal water unless otherwise specified.
The sources of the raw materials involved in the examples of the present application are as follows:
I. battery preparation
Example 1:
step 1: preparation of positive electrode active material
Step S1: preparation of Fe, co, V and S Co-doped manganese oxalate
689.6g of manganese carbonate, 455.27g of ferrous carbonate, 4.65g of cobalt sulfate and 4.87g of vanadium dichloride are added to a mixer and thoroughly mixed for 6 hours. And transferring the obtained mixture into a reaction kettle, adding 5L of deionized water and 1260.6g of oxalic acid dihydrate, heating to 80 ℃, fully stirring for 6 hours at a rotation speed of 500rpm, and uniformly mixing until no bubbles are generated during the reaction termination, thus obtaining Fe, co and V Co-doped manganese oxalate suspension. The suspension was then filtered, dried at 120℃and sanded to give manganese oxalate particles having a particle size of 100 nm.
Step S2: preparation of inner core Li 0.997 Mn 0.60 Fe 0.393 V 0.004 Co 0.003 P 0.997 S 0.003 O 4
1793.1g of the manganese oxalate prepared in (1) and 368.3g of lithium carbonate, 1146.6g of ammonium dihydrogen phosphate and 4.9g of dilute sulfuric acid were taken, added to 20L of deionized water, stirred well, and reacted at 80℃for 10 hours with uniform mixing to obtain a slurry. And transferring the slurry into spray drying equipment for spray drying granulation, and drying at the temperature of 250 ℃ to obtain powder. Sintering the powder in a roller kiln for 4 hours at 700 ℃ in a protective atmosphere (90% nitrogen and 10% hydrogen) to obtain the core material.
Step S3: preparation of first coating layer suspension
Preparation of Li 2 FeP 2 O 7 Solution 7.4g of lithium carbonate, 11.6g of ferrous carbonate, 23.0g of monoammonium phosphate and 12.6g of oxalic acid dihydrate were dissolved in 500mL of deionized water, the pH was controlled to 5, and then stirred and reacted at room temperature for 2 hours to obtain a solution, after which the solution was heated to 80 ℃ and maintained at this temperature for 4 hours to obtain a first clad layer suspension.
Step S4: coating of the first coating layer
Adding 1571.9g of doped lithium manganese phosphate core material obtained in the step S2 into the first coating layer suspension (the content of coating substances is 15.7 g) obtained in the step S3, fully stirring and mixing for 6h, transferring into a 120 ℃ oven for drying for 6h after uniformly mixing, and then sintering for 6h at 650 ℃ to obtain the pyrophosphate coated material.
Step S5: preparation of second coating layer suspension
3.7g of lithium carbonate, 11.6g of ferrous carbonate, 11.5g of monoammonium phosphate and 12.6g of oxalic acid dihydrate were dissolved in 1500mL of deionized water, and then stirred and reacted for 6 hours to obtain a solution, after which the solution was heated to 120 ℃ and maintained at that temperature for 6 hours to obtain a second coating layer suspension.
Step S6: cladding of the second cladding layer
And (3) adding 1586.8g of the pyrophosphate coated material obtained in the step (S4) into the second coating layer suspension (the content of coating substances is 47.1 g) obtained in the step (S5), fully stirring and mixing for 6 hours, uniformly mixing, transferring into a 120 ℃ oven for drying for 6 hours, and sintering at 700 ℃ for 8 hours to obtain the two-layer coated material.
Step S7: preparation of the aqueous solution of the third coating layer
37.3g of sucrose was dissolved in 500g of deionized water, followed by stirring and sufficient dissolution to obtain an aqueous sucrose solution.
Step S8: coating of the third coating layer
1633.9g of the two-layer coated material obtained in the step S6 is added into the sucrose solution obtained in the step S7, stirred and mixed for 6 hours, and after being uniformly mixed, the mixture is transferred into a baking oven at 150 ℃ to be dried for 6 hours, and then sintered for 10 hours at 700 ℃ to obtain the three-layer coated material.
Step 2: preparation of positive electrode plate
The prepared three-layer coated positive electrode active material, the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are mixed according to the weight ratio of 97.0:1.2:1.8 adding the mixture into N-methyl pyrrolidone (NMP), and uniformly stirring and mixing the mixture to obtain positive electrode slurry. The positive electrode slurry was then stirred at a concentration of 0.280g/1540.25mm 2 Uniformly coating the aluminum foil, and drying, cold pressing and cutting to obtain the positive electrode plate.
Step 3: preparation of negative electrode plate
The negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder Styrene Butadiene Rubber (SBR) and thickener sodium carboxymethyl cellulose (CMC) are mixed according to the weight ratio of 90:5:2:2: 1 is dissolved in deionized water, and the negative electrode slurry is prepared after stirring and mixing uniformly. The negative electrode slurry was prepared at a rate of 0.117g/1540.25mm 2 Uniformly coating the anode current collector copper foil, and drying, cold pressing and cutting to obtain the anode pole piece.
Step 4: preparation of electrolyte
In an argon atmosphere glove box (H 2 O<0.1ppm，O 2 <0.1 ppm), the organic solvent Ethylene Carbonate (EC)/ethylmethyl carbonate (EMC) was mixed uniformly in a volume ratio of 3/7, and 12.5% by weight (based on the weight of ethylene carbonate/ethylmethyl carbonate solvent) of LiPF was added 6 Dissolving in the organic solvent, and stirring uniformly to obtain electrolyte.
Step 5: preparation of a separator film
A commercially available PP-PE copolymer microporous film (from Zuo Hi-Tech Co., ltd., model 20) having a thickness of 20 μm and an average pore diameter of 80nm was used.
Step 6: preparation of full cell
And sequentially stacking the obtained positive pole piece, the isolating film and the negative pole piece, so that the isolating film is positioned in the middle of the positive pole and the negative pole to play a role in isolation, and winding to obtain the bare cell. The bare cell is placed in an outer package, the above electrolyte is injected and packaged, and a full battery (hereinafter also referred to as "full power") is obtained.
[ preparation of button cell ]
The positive electrode active material prepared above, polyvinylidene fluoride (PVDF), acetylene black were mixed at 90:5:5 weight ratio to N-methylpyrrolidone (NMP) and stirring in a drying room to prepare a slurry. Coating the slurry on an aluminum foil, drying and cold pressing to obtain the positive electrode plate. Coating amount was 0.2g/cm 2 A compaction density of 2.0g/cm 3 。
Lithium sheet is used as negative electrode, liPF of 1mol/L is used 6 In the volume ratio of 1:1:1 Ethylene Carbonate (EC) and dicarbonateThe solutions in ethyl ester (DEC) and dimethyl carbonate (DMC) are used as an electrolyte, and assembled together with the positive electrode sheet prepared as described above in a battery box to form a battery (hereinafter also referred to as "battery").
Examples 2 to 27 and comparative examples 1 to 19
The positive electrode active materials and batteries in examples 2 to 27 and comparative examples 1 to 19 were prepared in a similar manner to example 1, except for the differences in the preparation of the positive electrode active materials, see tables 1 to 6, in which comparative examples 1 to 2, 4 to 10 and 12 were not coated with the first layer, and thus there were no steps S3, S4; comparative examples 1-11 did not coat the second layer and therefore did not have steps S5-S6.
Note that: in all examples and comparative examples herein, the first cladding material and/or the second cladding material used, if not indicated, are crystalline by default.
Table 1: raw materials for preparing inner core
II. Evaluation of Performance
1. Lattice change rate test method:
the positive electrode active material sample is placed in XRD (model Bruker D8 Discover) under the constant temperature environment of 25 ℃, the sample is tested by adopting 1 DEG/min, the test data are subjected to finishing analysis, and the standard PDF card is referred to, so that lattice constants a0, b0, c0 and v0 (a 0, b0 and c0 represent the length of each aspect of the unit cell, v0 represents the unit cell volume, and the unit cell volume can be directly obtained through XRD finishing results) are calculated.
The positive electrode active material sample was prepared into a snap-on using the snap-on preparation method in the above example, and the snap-on was charged at a small rate of 0.05C until the current was reduced to 0.01C. And then taking out the positive pole piece in the buckling process, and soaking the positive pole piece in dimethyl carbonate (DMC) for 8 hours. Then drying, scraping powder, and screening out particles with the particle size smaller than 500 nm. The sample was taken and its unit cell volume v1 was calculated in the same manner as the above-described test fresh sample, and (v 0-v 1)/v0×100% was shown as the lattice change rate before and after the complete lithium intercalation (unit cell volume change rate) thereof.
Li/Mn dislocation defect concentration
The XRD results tested in the "lattice change rate measurement method" were compared with PDF (Powder Diffraction File) cards of standard crystals to obtain the Li/Mn inversion defect concentration. Specifically, XRD results tested in the lattice change rate measurement method are imported into General Structural Analysis System (GSAS) software, the refined results are automatically obtained, the occupation conditions of different atoms are contained, and the Li/Mn inversion defect concentration is obtained by reading the refined results.
3. Density of compaction
5g of the positive electrode active material powder obtained above was placed in a compaction dedicated mold (U.S. CARVER mold, model 13 mm), and then the mold was placed on a compaction density apparatus. The thickness of the powder under pressure (thickness after pressure relief) was read on the apparatus by applying a pressure of 3T, and the compaction density was calculated by ρ=m/v using a small picture area 1540.25mm with an area value of standard 2 。
4.3C charge constant current ratio
The fresh full cells prepared in each of the above examples and comparative examples were left to stand for 5min at a constant temperature of 25℃and discharged to 2.5V at 1/3 ℃. Standing for 5min, charging to 4.3V according to 1/3C, and then charging to current of less than or equal to 0.05mA at constant voltage under 4.3V. Standing for 5min, and recording the charge capacity at this time as C0. Discharging to 2.5V according to 1/3C, standing for 5min, charging to 4.3V according to 3C, standing for 5min, and recording the charge capacity at this time as C1. The constant current ratio of 3C charging is C1/C0 multiplied by 100 percent.
The higher the 3C charge constant current ratio, the better the rate capability of the secondary battery.
5. Dissolution test of transition metal Mn (Mn site doped Fe)
The full cells prepared in the above examples and comparative examples, after cycling to capacity fade to 80% at 45 ℃, were discharged to a cut-off voltage of 2.0V using a 0.1C rate. Then the battery is disassembled, the negative pole piece is taken out, and the battery is positioned at the negative pole30 unit areas (1540.25 mm) are randomly taken on the pole piece 2 ) Inductively coupled plasma emission spectroscopy (ICP) was measured with an Agilent ICP-OES 730. The amount of Fe (if the Mn site of the positive electrode active material is doped with Fe) and Mn therein was calculated from the ICP result, thereby calculating the elution amount of Mn (and Mn site-doped Fe) after the cycle. The test standard is in accordance with EPA-6010D-2014.
6. Surface oxygen valence state
A sample of 5g of the positive electrode active material prepared above was prepared into a power button according to the power button preparation method described in the above examples. The buckling electricity is charged by adopting a small multiplying power of 0.05C until the current is reduced to 0.01C. And then taking out the positive pole piece in the buckling process, and soaking the positive pole piece in DMC for 8 hours. Then drying, scraping powder, and screening out particles with the particle size smaller than 500 nm. The resulting particles were measured with an electron energy loss spectrum (EELS, instrument model Talos F200S) to obtain an Energy Loss Near Edge Structure (ELNES) reflecting the state density and energy distribution of the elements. And according to the state density and the energy level distribution, the number of occupied electrons is calculated by integrating the valence state density data, so that the valence state of the charged surface oxygen is calculated.
7. Measurement of manganese and phosphorus in positive electrode active Material
5g of the positive electrode active material prepared above was dissolved in 100ml of reverse aqua regia (concentrated hydrochloric acid: concentrated nitric acid=1:3) (concentrated hydrochloric acid concentration to 37%, concentrated nitric acid concentration to 65%), the content of each element of the solution was tested by ICP, and then the content of manganese element or phosphorus element was measured and converted (amount of manganese element or phosphorus element/amount of positive electrode active material: 100%) to obtain the weight ratio thereof.
8. Method for measuring initial gram capacity of button cell
The button cells prepared in each of the above examples and comparative examples were charged to 4.3V at 0.1C, then charged to 0.05mA or less at constant voltage at 4.3V, left standing for 5min, and then discharged to 2.0V at 0.1C, at which time the discharge capacity was the initial gram capacity, denoted as D0.
10. Full cell 60 ℃ storage 30 days cell expansion test:
the full cells prepared in the above respective examples and comparative examples were stored in a 100% state of charge (SOC) at 60 ℃. Open Circuit Voltage (OCV) and internal ac resistance (IMP) of the cells were measured before, after and during storage to monitor SOC and measure cell volume. Wherein the full cells were taken out after 48 hours of each storage, were tested for Open Circuit Voltage (OCV), internal resistance (IMP) after 1 hour of standing, and were measured for cell volume by a drainage method after cooling to room temperature. The water draining method is to measure the gravity F of the cell independently by using the balance with dial data for automatic unit conversion 1 The cells were then fully placed in deionized water (density known as 1g/cm 3 ) In the process, the gravity F of the battery cell at the moment is measured 2 Buoyancy force F applied to battery cell Floating device Namely F 1 -F 2 Then according to Archimedes principle F Floating device ＝ρ×g×V Row of rows Calculating to obtain the volume V= (F) 1 -F 2 )/(ρ×g)。
From the results of the OCV and IMP tests, the battery of all examples always maintained more than 99% SOC during the test until the end of storage.
After 30 days of storage, the cell volume was measured and the percentage increase in cell volume after storage was calculated relative to the cell volume before storage.
11. Full cell cycle performance test at 45 DEG C
Charging to 4.3V at 1C under constant temperature of 45 deg.C and 2.5-4.3V, then charging to current of 0.05mA or less at constant voltage of 4.3V, standing for 5min, discharging to 2.5V at 1C, and recording as D n (n=0, 1,2, … …). The above procedure was repeated until the capacity fade (fade) was reached to 80%, and the number of repetitions at this time was recorded, i.e., the number of cycles corresponding to 80% capacity retention at 45 ℃.
12. Interplanar spacing and angle testing
Taking 1g of each positive electrode active material powder prepared above, putting the powder into a 50mL test tube, injecting 10mL of 75% alcohol into the test tube, fully stirring and dispersing for 30 minutes, then taking a proper amount of the solution by using a clean disposable plastic suction tube, dripping the solution onto a 300-mesh copper mesh, at the moment, part of the powder remains on the copper mesh, transferring the copper mesh together with a sample into a TEM (Talos F200s G2) sample cavity for testing, obtaining a TEM test original picture, and storing an original picture format (xx.dm 3).
And opening the original picture obtained by the TEM test in digital micro software, performing Fourier transform (automatically completing by the software after clicking operation) to obtain a diffraction pattern, measuring the distance from a diffraction spot to the central position in the diffraction pattern, and obtaining the interplanar spacing and calculating the included angle according to a Bragg equation.
And comparing the obtained interplanar spacing and corresponding included angle data with the standard value of the interplanar spacing and corresponding included angle data, and identifying different substances of the coating layer.
13. Coating thickness test
Thickness test of coating layer mainly cuts a sheet with thickness of about 100nm from the middle of the single particle of the positive electrode active material prepared by FIB, then carries out TEM test on the sheet to obtain a TEM test original picture, and stores an original picture format (xx.dm 3).
And opening the original picture obtained by the TEM test in digital micro software, identifying the coating layer through lattice spacing and included angle information, and measuring the thickness of the coating layer.
The thickness was measured at three locations for the selected particles and averaged.
14. Determination of the molar ratio of SP2 morphology and SP3 morphology in the third layer coated carbon
The test was performed by Raman (Raman) spectroscopy. By peak separation of the Raman spectrum, id/Ig was obtained, where Id is the peak intensity of SP 3-form carbon and Ig is the peak intensity of SP 2-form carbon, and the molar ratio of the two was confirmed.
The results of the performance tests for all examples and comparative examples are presented in the table below.
Compaction density) and the prepared battery performance (electric capacity, high temperature cycle performance, high temperature storage performance) are excellent.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (26)
- A positive electrode active material having a core-shell structure includes a core and a shell coating the core,the chemical formula of the inner core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S;The values of x, y and z satisfy the following condition: keeping the whole kernel electrically neutral;the shell includes a first cladding layer that coats the inner core, a second cladding layer that coats the first cladding layer, and a third cladding layer that coats the second cladding layer, wherein,the first cladding layer comprises crystalline cokePhosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c Wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 6, and the values of a, b and c meet the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c The electric neutrality is maintained and the electric power is controlled,the crystalline pyrophosphates Li a MP 2 O 7 And M b (P 2 O 7 ) c Each M in (2) is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al,the second coating layer comprises crystalline phosphate XPO 4 Wherein, X is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;the third coating layer is carbon.
- The positive electrode active material having a core-shell structure according to claim 1, wherein,the range of the interplanar spacing of the crystalline pyrophosphate in the first coating layer is 0.293-0.470nm, and the included angle of the crystal direction (111) is 18.00-32.00 degrees; the crystal-state phosphate in the second coating layer has a interplanar spacing range of 0.244-0.425nm and an included angle of the crystal direction (111) of 20.00-37.00 degrees.
- The positive electrode active material having a core-shell structure according to claim 1 or 2, wherein in the core, a ratio of y to 1-y is 1:10 to 1:1, alternatively 1:4 to 1:1.
- the positive electrode active material having a core-shell structure according to any one of claims 1 to 4, wherein, in the core, a ratio of z to 1-z is 1:9 to 1:999, alternatively 1:499 to 1:249.
- the cathode active material having a core-shell structure according to any one of claims 1 to 4, wherein the carbon of the third coating layer is a mixture of SP2 morphology carbon and SP3 morphology carbon, optionally the molar ratio of SP2 morphology carbon to SP3 morphology carbon is any value in the range of 0.1 to 10, optionally any value in the range of 2.0 to 3.0.
- The positive electrode active material having a core-shell structure according to any one of claims 1 to 5, wherein,the first cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, and more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core; and/orThe second cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, more alternatively from 2 to 4 wt%, based on the weight of the core; and/orThe third cladding layer is present in an amount of greater than 0 and less than or equal to 6 wt%, alternatively greater than 0 and less than or equal to 5.5 wt%, and more alternatively greater than 0 and less than or equal to 2 wt%, based on the weight of the core.
- The positive electrode active material having a core-shell structure according to any one of claims 1 to 6, wherein a thickness of the first coating layer is 1 to 10nm; and/orThe thickness of the second coating layer is 2-15nm; and/orThe thickness of the third coating layer is 2-25nm.
- The positive electrode active material having a core-shell structure according to any one of claims 1 to 7, wherein,the manganese element content is in the range of 10 wt% to 35 wt%, alternatively in the range of 15 wt% to 30 wt%, more alternatively in the range of 17 wt% to 20 wt%, the phosphorus element content is in the range of 12 wt% to 25 wt%, alternatively in the range of 15 wt% to 20 wt%, and the weight ratio of manganese element to phosphorus element is in the range of 0.90 to 1.25, alternatively 0.95 to 1.20, based on the weight of the positive electrode active material.
- The positive electrode active material with a core-shell structure according to any one of claims 1 to 8, wherein the positive electrode active material with a core-shell structure has a lattice change rate of 4% or less, optionally 3.8% or less, more optionally 2.0 to 3.8% before and after complete lithium deintercalation.
- The positive electrode active material with a core-shell structure according to any one of claims 1 to 9, wherein the Li/Mn dislocation defect concentration of the positive electrode active material with a core-shell structure is 4% or less, alternatively 2.2% or less, more alternatively 1.5 to 2.2%.
- The positive electrode active material with a core-shell structure according to any one of claims 1 to 10, wherein the positive electrode active material with a core-shell structure has a compacted density of 2.2g/cm at 3T 3 Above, optionally 2.2g/cm 3 Above and 2.8g/cm 3 The following is given.
- The cathode active material with a core-shell structure according to any one of claims 1 to 11, wherein the surface oxygen valence state of the cathode active material with a core-shell structure is-1.90 or less, optionally-1.90 to-1.98.
- A method for preparing a positive electrode active material, comprising the steps of:providing a core material: the chemical formula of the inner core is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, and A is selected fromZn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, wherein R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S;And (3) coating: respectively provide Li a MP 2 O 7 And/or M b (P 2 O 7 ) c XPO 4 Adding the core material into the suspension, mixing, and sintering to obtain the positive electrode active material, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 4, c is more than or equal to 1 and less than or equal to 6, and the values of a, b and c meet the following conditions: crystalline pyrophosphates Li a MP 2 O 7 Or M b (P 2 O 7 ) c Keeping electric neutrality; each M is independently one or more elements selected from Fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al; x is one or more elements selected from Li, fe, ni, mg, co, cu, zn, ti, ag, zr, nb or Al;wherein the positive electrode active material has a core-shell structure including the core and a shell coating the core, the shell including a first coating layer coating the core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer, the first coating layer including crystalline pyrophosphate Li a MP 2 O 7 And/or M b (P 2 O 7 ) c The second coating layer comprises crystalline phosphate XPO 4 The third coating layer is carbon.
- The method for preparing a positive electrode active material according to claim 13, the step of providing a core material comprising the steps of:step (1): mixing and stirring a manganese source, an element A doping agent and acid in a container to obtain manganese salt particles doped with the element A;Step (2): mixing the manganese salt particles doped with the element A with a lithium source, a phosphorus source and a doping agent of the element R in a solvent to obtain slurry, and sintering under the protection of inert gas atmosphere to obtain an inner core doped with the element A and the element R, wherein the inner core doped with the element A and the element R is Li 1+x Mn 1-y A y P 1-z R z O 4 Wherein x is any number in the range of-0.100 to 0.100, y is any number in the range of 0.001 to 0.500, z is any number in the range of 0.001 to 0.100, a is one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge, optionally Fe, ti, V, ni, co and Mg, R is one or more elements selected from B, si, N and S, optionally R is one element selected from B, si, N and S.
- The method for preparing a positive electrode active material according to claim 14, wherein,the step (1) is carried out at a temperature of 20-120 ℃, optionally 40-120 ℃; and/orThe stirring in step (1) is carried out at 400-700rpm for 1-9 hours, optionally 3-7 hours.
- The method for preparing a positive electrode active material according to claim 14, wherein the step (2) is performed at a temperature of 20 to 120 ℃, optionally 40 to 120 ℃, for 1 to 10 hours.
- The method for producing a positive electrode active material according to any one of claims 14 to 16, wherein,the doping agent of the element A is one or more of simple substance, carbonate, sulfate, chloride, nitrate, organic acid salt, oxide and hydroxide of one or more elements selected from Zn, al, na, K, mg, mo, W, ti, V, zr, fe, ni, co, ga, sn, sb, nb and Ge respectively; and/or the number of the groups of groups,the doping agent of the element R is one or more of inorganic acid, organic acid, sulfate, chloride, nitrate, organic acid salt, oxide and hydroxide of one or more elements selected from B, si, N and S respectively.
- The method for producing a positive electrode active material according to any one of claims 13 to 17, wherein the coating step includes:a first coating step: dissolving a source of element M, a phosphorus source, an acid and optionally a lithium source in a solvent to obtain a first coating layer suspension; fully mixing the inner core obtained in the inner core step with the first coating layer suspension obtained in the first coating step, drying, and then sintering to obtain a material coated by the first coating layer;and a second coating step: dissolving a source of element X, a phosphorus source and an acid in a solvent to obtain a second coating layer suspension; fully mixing the material coated by the first coating layer obtained in the first coating step with the second coating layer suspension obtained in the second coating step, drying, and then sintering to obtain a material coated by two coating layers;And a third coating step: dissolving a carbon source in a solvent, and fully dissolving to obtain a third coating layer solution; and then adding the materials coated by the two coating layers obtained in the second coating step into the third coating layer solution, uniformly mixing, drying, and sintering to obtain the material coated by the three coating layers, namely the positive electrode active material.
- The method for preparing a positive electrode active material according to claim 18, wherein,in the first coating step, the pH of the solution in which the source of element M, the source of phosphorus and the acid and optionally the source of lithium are dissolved is controlled to 3.5-6.5, then stirred and reacted for 1-5 hours, then the solution is warmed to 50-120 ℃ and kept at that temperature for 2-10 hours, and/or,the sintering is carried out at 650-800 ℃ for 2-6 hours.
- The method for producing a positive electrode active material according to any one of claims 18 to 19, wherein,in the second coating step, after dissolving the source of element X, the phosphorus source and the acid in the solvent, stirring and reacting for 1-10 hours, then heating the solution to 60-150 ℃, and maintaining the temperature for 2-10 hours, and/or,sintering is carried out at 500-700 ℃ for 6-10 hours.
- The method for producing a positive electrode active material according to any one of claims 18 to 20, wherein the sintering in the third coating step is performed at 700 to 800 ℃ for 6 to 10 hours.
- A positive electrode sheet comprising a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer comprising the positive electrode active material having a core-shell structure according to any one of claims 1 to 12 or the positive electrode active material prepared by the positive electrode active material preparation method according to any one of claims 13 to 21, and the content of the positive electrode active material in the positive electrode film layer being 90 to 99.5 wt%, optionally 95 to 99.5 wt%, based on the total weight of the positive electrode film layer.
- A secondary battery comprising the positive electrode active material having a core-shell structure according to any one of claims 1 to 12 or the positive electrode active material prepared by the positive electrode active material preparation method according to any one of claims 13 to 21 or the positive electrode sheet according to claim 22.
- A battery module comprising the secondary battery according to claim 23.
- A battery pack comprising the battery module of claim 24.
- An electric device comprising at least one selected from the secondary battery of claim 23, the battery module of claim 24, or the battery pack of claim 25.
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| CN116779826A (en) * | 2023-07-28 | 2023-09-19 | 宁波容百新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN117117153B (en) * | 2023-10-16 | 2024-02-20 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof and lithium ion battery |
| CN117594771B (en) * | 2023-12-01 | 2024-04-19 | 山西华钠铜能科技有限责任公司 | Sodium-electricity positive electrode material and preparation method thereof |
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| CN106058220B (en) * | 2016-08-12 | 2019-07-12 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of titanium nitride and carbon dual cladding iron manganese phosphate for lithium composite material |
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| CN109560266A (en) * | 2018-11-07 | 2019-04-02 | 湖北锂诺新能源科技有限公司 | The preparation method of the lithium ferric manganese phosphate positive electrode of lithium metaaluminate cladding |
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