CN117239087A - Modified ternary positive electrode material and preparation method thereof - Google Patents
Modified ternary positive electrode material and preparation method thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 44
- 239000010452 phosphate Substances 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims abstract description 20
- 229940075613 gadolinium oxide Drugs 0.000 claims abstract description 20
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- -1 nickel-cobalt-aluminum Chemical compound 0.000 claims abstract description 13
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- 239000010406 cathode material Substances 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 230000006978 adaptation Effects 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 34
- 239000000463 material Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 125000005341 metaphosphate group Chemical group 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- QAISYPNSOYCTPY-UHFFFAOYSA-N cerium(3+) gadolinium(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Ce+3].[Gd+3] QAISYPNSOYCTPY-UHFFFAOYSA-N 0.000 description 1
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a modified ternary positive electrode material, which takes a nickel-cobalt-aluminum ternary positive electrode material or a nickel-cobalt-manganese ternary positive electrode material as a matrix, wherein phosphate is doped in the matrix, and Ce is coated on the outer surface of the matrix x Gd 2‑2x O 3‑x A layer. The preparation method comprises the following steps: weighing and mixing a ternary positive electrode material precursor, a lithium source and a phosphorus source to obtain a mixture; sintering the mixture for the first time to obtain a phosphate doped ternary anode material; the saidAnd mixing the phosphate doped ternary anode material with cerium oxide and gadolinium oxide, and then performing secondary sintering to obtain the modified ternary anode material. The invention dopes phosphate in the matrix of the ternary positive electrode material, and the outer surface of the matrix is coated with Ce x Gd 2‑2x O 3‑x The layer, the two mutually support, can improve the not enough of current ternary positive electrode material overcharge safety for positive electrode material can better adaptation some extreme conditions, avoids the potential safety hazard in the application process.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a phosphate doped and rare earth coated ternary positive electrode material and a preparation method thereof.
Background
The lithium ion battery is used as one of the secondary reversible green energy sources, the development of the lithium ion battery is greatly dependent on the continuous improvement of the performance of the positive electrode material, and the quality of the overcharge performance of the positive electrode material has an important influence on the safety of the lithium ion battery. The existing ternary positive electrode material has the defect in the aspect of overcharge safety, when a battery is charged to a higher voltage, particularly under the overcharge condition, the structure of the ternary positive electrode material is unstable due to the overlarge lithium removal amount of the positive electrode material, and a large amount of active oxygen is generated by O 2 Form release, accompanied by heat release, O 2 Side reactions are carried out with electrolyte and a battery cathode successively to generate heat, so that the final battery is easy to be out of control and explode. The method for slowing down the over-charging and oxygen release of the positive electrode material is one of effective measures for improving the safety of the lithium ion battery, and the current method for slowing down the over-charging and oxygen release of the positive electrode material comprises the steps of modifying the surface and the bulk phase of the positive electrode material, which correspond to the improvement of the early stage and the later stage of the over-charging of the battery respectively.
Chinese patent publication No. CN110061203a discloses a rare earth composite metaphosphate coated lithium positive electrode material and a preparation method thereof, the method comprises the following steps: and fully ball-milling and mixing the lithium anode material and the rare earth composite metaphosphate, and calcining at high temperature, grinding and sieving to obtain the rare earth composite metaphosphate coated lithium anode material. According to the method, the surface of the lithium anode material can be prevented from being corroded by electrolyte through rare earth composite metaphosphate coating, so that the lithium anode material has better cycle performance and thermal stability under the voltage of 4.50V or even higher. However, the positive electrode material is in an overcharged condition,and when the lithium removal degree is continuously increased, the material structure damage degree and the oxygen release phenomenon can gradually extend to the inside of the bulk phase, and the side reaction is aggravated. The Chinese patent publication No. CN112038612A discloses a boron-doped phosphite coated nickel-based positive electrode material for a lithium ion all-solid battery, a preparation method and application thereof, wherein the method comprises the steps of coating the surface of the boron-doped nickel-based positive electrode material for the lithium ion battery with phosphite, wherein the surface is coated with a polyanion salt compound LiLa 1-y M y (PO 3 ) 4 The compound is favorable for improving the stability of an interface and the lithium ion transmission capability, but has lower electronic conductivity, and has certain limitation in the application of the compound in the current large-scale lithium ion battery which takes liquid organic electrolyte as a component. In addition, for the ternary positive electrode material deeply delithiated, high-activity Ni 4+ Electrons are often captured in lattice oxygen to aggravate cation mixing, the material structure is subjected to phase change and releases oxygen to generate heat, thermal runaway is caused, and a polyanion salt compound LiLa is coated on the surface 1-y M y (PO 3 ) 4 Since La has few highly orbital extra-nuclear electrons, it has no remarkable effect in stabilizing lattice oxygen finally.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified ternary positive electrode material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a modified ternary positive electrode material takes a nickel-cobalt-aluminum ternary positive electrode material or a nickel-cobalt-manganese ternary positive electrode material as a matrix, phosphate is doped in the matrix, and Ce is coated on the outer surface of the matrix x Gd 2- 2x O 3-x And a layer, wherein x is more than or equal to 0.4 and less than or equal to 0.8.
In the modified ternary cathode material, preferably, the doping mole amount of the P element in the phosphate accounts for 0.05% -3% of the total mole number of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary cathode material, or the doping mole amount of the P element in the phosphate accounts for 0.05% -3% of the total mole number of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary cathode material.
In the modified ternary cathode material, preferably, the doping mole amount of the P element in the phosphate accounts for 0.1% -1% of the total mole number of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary cathode material, or the doping mole amount of the P element in the phosphate accounts for 0.1% -0.4% of the total mole number of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary cathode material.
The modified ternary positive electrode material is preferably that x is more than or equal to 0.5 and less than or equal to 0.6.
The invention also provides a preparation method of the modified ternary cathode material, which comprises the following steps of:
(1) Weighing and mixing a ternary positive electrode material precursor, a lithium source and a phosphorus source to obtain a mixture;
(2) Sintering the mixture for the first time to obtain a phosphate doped ternary anode material;
(3) And mixing the phosphate doped ternary anode material with cerium oxide and gadolinium oxide, and then performing secondary sintering to obtain the modified ternary anode material.
In the above preparation method, preferably, in the step (1), the lithium source is one or more selected from anhydrous lithium hydroxide and lithium hydroxide monohydrate; the phosphorus source is selected from one or more of diammonium hydrogen phosphate, monoammonium phosphate, aluminum phosphate and lithium phosphate.
In the above preparation method, preferably, in the step (1), the molar ratio of the lithium source to the ternary cathode material precursor is 0.9-1.2.
In the above preparation method, preferably, in the step (2), the primary sintering is performed in an oxygen atmosphere, and the primary sintering temperature is 720-780 ℃ and the time is 8-20h.
In the above preparation method, preferably, in the step (3), the molar addition amounts of the cerium oxide and the gadolinium oxide are respectively 0.025% -0.035% and 0.015% -0.025% of the total molar amounts of nickel, cobalt and aluminum in the phosphate doped ternary cathode material matrix; or 0.025% -0.035% and 0.015% -0.025% of total mole of nickel, cobalt and manganese in the phosphate doped ternary positive electrode material matrix respectively.
In the above preparation method, preferably, in the step (3), the secondary sintering is performed in an oxygen atmosphere, and the temperature of the secondary sintering is 640-690 ℃ and the time is 3-12h. When the sintering temperature is too low, cerium oxide and gadolinium oxide mainly exist in a floating powder form on the surface of the material, and the cerium oxide and the gadolinium oxide are more difficult to be doped into crystal lattices of each other due to insufficient temperature, and more exist in cerium oxide and gadolinium oxide crystal phases; cerium oxide and gadolinium oxide may also form Ce during the heat preservation when the sintering temperature is too high x Gd 2-2x O 3-x The structure, however, due to the too high sintering temperature, can continuously enter the matrix phase and is equivalent to the doping of conventional elements, so that pure Ce can not exist on the surface of the matrix x Gd 2-2x O 3-x The coating layer lacks abundant oxygen vacancies, so that the better oxygen fixation aim cannot be achieved, and the hidden danger of oxygen release still exists during overcharging.
Compared with the prior art, the invention has the advantages that:
(1) The surface of the ternary positive electrode material matrix is coated with Ce x Gd 2-2x O 3-x The coating layer has rich oxygen vacancies, and by capturing active oxygen ions on the surface of the material, the activation energy of lattice oxygen loss is increased, the release of lattice oxygen and heat release caused by excessive lithium removal during overcharging are relieved, and the corrosion of electrolyte to a lithium positive electrode material and other side reaction heat release are reduced, so that the integral temperature rise of a battery cell in the later stage of overcharging is reduced, and the use safety of the battery cell is enhanced; on the other hand, during sintering Ce x Gd 2-2x O 3-x Part of Ce in the coating 4+ And Gd 3+ Can be dispersed into the crystal lattice of the ternary positive electrode material, reduces lithium nickel mixed discharge, forms stronger Ce-O, gd-O bond, and can furthest reduce the damage of the near-surface structure of the positive electrode material.
(2) According to the invention, phosphate is doped in the ternary positive electrode material matrix, and the phosphate contains stable P-O bonds, so that P element in the phosphate is doped into the material and is easily combined with bulk lattice oxygen to form bonds, and the stability of bulk structure of the material during overcharging is facilitated.
(3) The phosphates in the present invention belong toIncomplete doping, little residue after sintering is left on the surface of the substrate, and Ce is respectively mixed with the substrate during the secondary sintering process x Gd 2-2x O 3-x Ce of (a) 3+ 、Gd 3+ Bind to form LiGdP 2 O 7 、LiCeP 2 O 7 The structure has better ionic conductivity and is beneficial to Li + Can prevent the surface of the positive electrode material from being corroded by electrolyte, and further improves the thermal stability and safety of the positive electrode material.
(4) The preparation process is simple to operate and has low requirements on production equipment.
In conclusion, the invention dopes phosphate in the matrix of the ternary positive electrode material, and the outer surface of the matrix is coated with Ce x Gd 2-2x O 3-x The layer, the two mutually support, can improve the not enough of current ternary positive electrode material overcharge safety for positive electrode material can better adaptation some extreme conditions, avoids the potential safety hazard in the application process.
Drawings
FIG. 1 is an electron microscopic view of a modified ternary cathode material prepared in example 1 of the present invention;
FIG. 2 is an electron microscopic view of the ternary positive electrode material prepared in comparative example 1 of the present invention;
FIG. 3 is an EPMA image of the distribution of the P element corresponding to the cross section of the secondary sphere of the modified ternary cathode material prepared in example 1;
fig. 4 is a graph showing the change in cell surface temperature during charging of a soft pack cell prepared using the modified ternary cathode material of example 1, comparative example 1 of the present invention from 0% soc to 130% soc by a 1C constant current.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The various reagents and materials used in the present invention are commercially available or may be prepared by known methods unless otherwise specified.
Example 1:
the modified ternary positive electrode material of the invention is prepared from Li 1.03 Ni 0.9 Co 0.08 Al 0.02 P 0.003 O 2 The composite material is a matrix, phosphate is doped in the matrix, the doping mole number of P element in the phosphate accounts for 0.3 percent of the total mole number of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary positive electrode material, and the outer surface of the matrix is coated with Ce 0.6 Gd 0.8 O 2.4 A layer.
The preparation method of the modified ternary cathode material in the embodiment comprises the following steps:
(1) According to the mole ratio of Li: me=1.03 molar ratio of lithium hydroxide to ternary positive electrode precursor Ni 0.9 Co 0.08 Al 0.02 (OH) 2 Weighing diammonium hydrogen phosphate according to the amount that the doping mole ratio of P in the ternary positive electrode material matrix is 0.3% of Me, and uniformly mixing the weighed materials, wherein Me refers to nickel, cobalt and aluminum;
(2) Placing the mixed material obtained in the step (1) into an oxygen atmosphere furnace for primary sintering, preserving heat for 12 hours at 760 ℃, and then cooling and sieving along with the furnace to obtain a phosphate doped ternary positive electrode material matrix;
(3) Uniformly mixing the material obtained in the step (2) with cerium oxide and gadolinium oxide, wherein the molar addition of the cerium oxide and the gadolinium oxide is respectively 0.03 percent and 0.02 percent of the total molar amount of nickel, cobalt and aluminum in a phosphate doped ternary cathode material matrix;
(4) And (3) putting the mixed material obtained in the step (3) into an oxygen atmosphere furnace for secondary sintering, preserving heat for 8 hours at 680 ℃ after secondary sintering, and then cooling and sieving along with the furnace to obtain a modified ternary cathode material finished product.
Example 2:
the modified ternary positive electrode material of the invention comprisesThe primary positive electrode material is nickel-cobalt-aluminum ternary positive electrode material Li 1.03 Ni 0.9 Co 0.08 Al 0.02 P 0.005 O 2 The composite material is a matrix, phosphate is doped in the matrix, the doping mole number of P element in the phosphate accounts for 0.5 percent of the total mole number of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary positive electrode material, and the outer surface of the matrix is coated with Ce 0.7 Gd 0.6 O 2.3 A layer.
The preparation method of the modified ternary cathode material in the embodiment comprises the following steps:
(1) According to the mole ratio of Li: me=1.03 molar ratio of lithium hydroxide to ternary positive electrode precursor Ni 0.9 Co 0.08 Al 0.02 (OH) 2 Weighing diammonium hydrogen phosphate according to the doping mole ratio of P in the ternary positive electrode material matrix accounting for 0.5% of Me, and uniformly mixing the weighed materials, wherein Me refers to nickel, cobalt and aluminum;
(2) Placing the mixed material obtained in the step (1) into an oxygen atmosphere furnace for primary sintering, preserving heat at 780 ℃ for 12 hours, and then cooling and sieving along with the furnace to obtain a phosphate doped ternary anode material matrix;
(3) Uniformly mixing the material obtained in the step (2) with cerium oxide and gadolinium oxide, wherein the molar addition amounts of the cerium oxide and the gadolinium oxide are respectively 0.035% and 0.015% of the total molar amounts of nickel, cobalt and aluminum in the phosphate doped ternary cathode material matrix;
(4) And (3) putting the mixed material obtained in the step (3) into an oxygen atmosphere furnace for secondary sintering, preserving heat for 8 hours at 690 ℃ after secondary sintering, and then cooling and sieving along with the furnace to obtain a modified ternary cathode material finished product.
Example 3:
the modified ternary positive electrode material is prepared from nickel-cobalt-manganese ternary positive electrode material Li 1.03 Ni 0.9 Co 0.08 Al 0.02 P 0.0005 O 2 The composite material is a matrix, phosphate is doped in the matrix, the doping mole number of P element in the phosphate accounts for 0.05 percent of the total mole number of nickel, cobalt and aluminum in the nickel-cobalt-manganese ternary positive electrode material, and the outer surface of the matrix is coated with Ce 0.5 GdO 2.5 A layer.
The preparation method of the modified ternary cathode material in the embodiment comprises the following steps:
(1) According to the mole ratio of Li: me=1.03 molar ratio of lithium hydroxide to ternary positive electrode precursor Ni 0.9 Co 0.08 Al 0.02 (OH) 2 Weighing diammonium hydrogen phosphate according to the doping mole ratio of P in the ternary positive electrode material matrix accounting for 0.05% of Me, and uniformly mixing the weighed materials, wherein Me refers to nickel, cobalt and aluminum;
(2) Placing the mixed material obtained in the step (1) into an oxygen atmosphere furnace for primary sintering, preserving heat at 720 ℃ for 12 hours, and then cooling and sieving along with the furnace to obtain a phosphate doped ternary anode material matrix;
(3) Uniformly mixing the material obtained in the step (2) with cerium oxide and gadolinium oxide, wherein the molar addition amounts of the cerium oxide and the gadolinium oxide are respectively 0.025% and 0.025% of the total molar amount of nickel, cobalt and aluminum in the phosphate doped ternary cathode material matrix;
(4) And (3) putting the mixed material obtained in the step (3) into an oxygen atmosphere furnace for secondary sintering, preserving heat for 8 hours at 640 ℃ after secondary sintering, and then cooling and sieving along with the furnace to obtain a modified ternary cathode material finished product.
Comparative example 1:
the difference between this comparative example and example 1 is that: and (3) adding no cerium oxide and gadolinium oxide in the step (1), and keeping other conditions consistent with those of the embodiment 1 to obtain a finished product of the ternary cathode material.
Comparative example 2:
the difference between this comparative example and example 1 is that: in the step (3), cerium oxide and gadolinium oxide are not added, and the outer surface of the matrix is Ce-free 0.6 Gd 0.8 O 2.4 The coating layer and other conditions were the same as in example 1 to obtain a phosphate-doped ternary cathode material finished product.
Comparative example 3:
the difference between this comparative example and example 1 is that: in the preparation process, the coating temperatures of cerium oxide and gadolinium oxide are different, namely the materials uniformly mixed in the step (4) are kept at 600 ℃ for 8 hours, and other conditions are kept consistent with those of the embodiment 1, so that the phosphate doped cerium gadolinium oxide coated ternary cathode material finished product is obtained.
Comparative example 4:
the difference between this comparative example and example 1 is that: in the preparation process, gadolinium oxide in the coating material is replaced by lanthanum oxide, and other conditions are kept consistent with those of the embodiment 1, so that the phosphate doped cerium-lanthanum oxide coated ternary positive electrode material is obtained.
The SEM picture of the modified cathode material obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the modified cathode material is formed by densely stacking primary particles to form secondary spheres, the surface is relatively coarse, and rare earth oxide nano particles are mainly deposited on the surface of the surface cathode material to form Ce x Gd 2-2x O 3-x And a coating layer. The EPMA image of the distribution of the P element in the section of the secondary sphere of the modified positive electrode material is shown in figure 3, the P element is mainly uniformly distributed in the secondary sphere, and a small amount of the P element is remained on the surface of the secondary sphere.
SEM pictures of the modified cathode material obtained in comparative example 1 are shown in fig. 2, and the secondary sphere surface is smooth and the primary particle boundary is clear because of the absence of the rare earth oxide coating layer.
The modified ternary cathode materials finally obtained in each example and comparative example are made into a soft package battery for evaluation test:
(1) 1C discharge and DCR test are carried out under the conditions of normal temperature and voltage interval of 2.8-4.2V, and the discharge capacity and initial DCR are recorded;
(2) Charging and discharging the soft-package battery cell at 1C/1C for one time under the condition of 2.8-4.2V, then charging the soft-package battery cell to 130% SOC at 1C constant current, detecting the temperature of the surface of the battery cell by a thermocouple, recording the maximum temperature reached by the surface of the battery cell, and observing the condition of the ignition of the battery cell, wherein the temperature change curve graphs of the battery cell surfaces of the embodiment 1 and the comparative example 1 are shown in fig. 4.
Specific data for the ternary cathode materials of the above examples and comparative examples are shown in table 1 below.
Table 1 properties of the modified ternary cathode materials in each of examples and comparative examples
As can be seen from Table 1, in examples 1-3, the phosphate was doped with Ce x Gd 2-2x O 3-x The overcharging cores coated with the ternary positive electrode material have no ignition, and the surface temperature of the battery core is better than that of comparative examples 1-4, which shows that the final preparation of the invention is phosphate doped and Ce x Gd 2-2x O 3-x The coated ternary positive electrode material has extremely excellent overcharge safety performance. In comparative example 3, cerium oxide and gadolinium oxide were used as the coating material, but the sintering temperature was too low and Ce was not formed x Gd 2-2x O 3-x Coating, but CeO 2 And Gd 2 O 3 As can be seen from experimental data, comparative example 3 shows that the surface temperature of the overcharge core is significantly higher than that of example 1, indicating Ce x Gd 2-2x O 3-x The overcharge safety of the coated ternary positive electrode material is superior to CeO 2 And Gd 2 O 3 And mixing the coated ternary positive electrode material. Compared with comparative example 1, the discharge capacity of comparative example 2 is not obviously lost, the overcharge core is not ignited, but the surface temperature of the battery core is still higher than that of the embodiment, so that the phosphate doping leads the P element to form a bond with the lattice oxygen of the positive electrode material, a certain stabilizing effect is achieved on the bulk structure of the material, collapse heat generation and other side reaction heat generation of the material structure during overcharging are reduced, and the effect of improving the overcharge safety is far less than that of the embodiment.
It can also be seen from the experimental data in Table 1 that the phosphate doping was combined with Ce x Gd 2-2x O 3-x The coating layer is beneficial to the improvement of the overcharge safety of the anode material, and the effect of the two materials existing at the same time is more remarkable. Comparative example 4 is compared with example 1, in which the cell was exploded by firing during overcharging, and lanthanum element in the coating layer was a rare earth element, but the number of electrons outside the high orbit core was far less than that of gadolinium element, and thus far inferior to example 1 in stabilizing lattice oxygen.
In conclusion, the invention dopes phosphate in the matrix of the ternary positive electrode material, and the outer surface of the matrix is coated with Ce x Gd 2-2x O 3-x Layers, which are matched with each other and canThe defect of overcharge safety of the existing ternary anode material is overcome, so that the anode material can be better adapted to some extreme conditions, and potential safety hazards in the application process are avoided.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the embodiments and the protection scope of the present invention, although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A modified ternary positive electrode material is characterized in that the modified ternary positive electrode material takes a nickel-cobalt-aluminum ternary positive electrode material or a nickel-cobalt-manganese ternary positive electrode material as a matrix, phosphate is doped in the matrix, and Ce is coated on the outer surface of the matrix x Gd 2-2x O 3-x And a layer, wherein x is more than or equal to 0.4 and less than or equal to 0.8.
2. The modified ternary cathode material of claim 1, wherein the doped molar amount of the P element in the phosphate is 0.05% -3% of the total molar amount of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary cathode material, or the doped molar amount of the P element in the phosphate is 0.05% -3% of the total molar amount of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary cathode material.
3. The modified ternary cathode material of claim 2, wherein the doped molar amount of the P element in the phosphate is 0.1% -1% of the total molar amount of nickel, cobalt and aluminum in the nickel-cobalt-aluminum ternary cathode material, or the doped molar amount of the P element in the phosphate is 0.1% -0.4% of the total molar amount of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary cathode material.
4. The modified ternary cathode material of claim 1, wherein x is 0.5-0.6.
5. A method for preparing the modified ternary cathode material according to any one of claims 1 to 4, comprising the steps of:
(1) Weighing and mixing a ternary positive electrode material precursor, a lithium source and a phosphorus source to obtain a mixture;
(2) Sintering the mixture for the first time to obtain a phosphate doped ternary anode material;
(3) And mixing the phosphate doped ternary anode material with cerium oxide and gadolinium oxide, and then performing secondary sintering to obtain the modified ternary anode material.
6. The method of claim 5, wherein in step (1), the lithium source is selected from one or both of anhydrous lithium hydroxide and lithium hydroxide monohydrate; the phosphorus source is selected from one or more of diammonium hydrogen phosphate, monoammonium phosphate, aluminum phosphate and lithium phosphate.
7. The method of claim 5, wherein in step (1), the molar ratio of the lithium source to the ternary positive electrode material precursor is 0.9-1.2.
8. The method according to claim 5, wherein in the step (2), the primary sintering is performed in an oxygen atmosphere at a temperature of 720 ℃ to 780 ℃ for 8 to 20 hours.
9. The method of claim 5, wherein in step (3), the molar addition amounts of the cerium oxide and the gadolinium oxide are respectively 0.025% -0.035% and 0.015% -0.025% of the total molar amounts of the nickel, cobalt and aluminum in the phosphate-doped ternary cathode material matrix, or are respectively 0.025% -0.035% and 0.015% -0.025% of the total molar amounts of the nickel, cobalt and manganese in the phosphate-doped ternary cathode material matrix.
10. The method according to claim 5, wherein in the step (3), the secondary sintering is performed in an oxygen atmosphere at a temperature of 640 to 690 ℃ for 3 to 12 hours.
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