CN117255150A - Composite positive electrode material, preparation method thereof and all-solid-state lithium battery containing composite positive electrode material - Google Patents
Composite positive electrode material, preparation method thereof and all-solid-state lithium battery containing composite positive electrode material Download PDFInfo
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- CN117255150A CN117255150A CN202310042179.6A CN202310042179A CN117255150A CN 117255150 A CN117255150 A CN 117255150A CN 202310042179 A CN202310042179 A CN 202310042179A CN 117255150 A CN117255150 A CN 117255150A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 13
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 45
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims abstract description 39
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 21
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims abstract description 6
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 13
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910020314 ClBr Inorganic materials 0.000 claims 1
- 239000007772 electrode material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 19
- 239000007787 solid Substances 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical group [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 1
- QMTITMYAGTWBKM-UHFFFAOYSA-N [O].[Zr].[La] Chemical compound [O].[Zr].[La] QMTITMYAGTWBKM-UHFFFAOYSA-N 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/18—Telephone sets specially adapted for use in ships, mines, or other places exposed to adverse environment
- H04M1/185—Improving the rigidity of the casing or resistance to shocks
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04B—TRANSMISSION
- H04B1/00—Details of transmission systems, not covered by a single one of groups H04B3/00 - H04B13/00; Details of transmission systems not characterised by the medium used for transmission
- H04B1/38—Transceivers, i.e. devices in which transmitter and receiver form a structural unit and in which at least one part is used for functions of transmitting and receiving
- H04B1/3816—Mechanical arrangements for accommodating identification devices, e.g. cards or chips; with connectors for programming identification devices
- H04B1/3818—Arrangements for facilitating insertion or removal of identification devices
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04M—TELEPHONIC COMMUNICATION
- H04M1/00—Substation equipment, e.g. for use by subscribers
- H04M1/02—Constructional features of telephone sets
- H04M1/0202—Portable telephone sets, e.g. cordless phones, mobile phones or bar type handsets
- H04M1/026—Details of the structure or mounting of specific components
-
- 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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- Engineering & Computer Science (AREA)
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- Computer Networks & Wireless Communication (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The present disclosure provides a composite positive electrode material, a method of preparing the same, and an all-solid-state lithium battery including the same. The composite anode material is of a core-shell structure and sequentially comprises nickel cobalt lithium manganate particles, a lithium niobate layer, a lithium phosphate layer and a sulfide solid electrolyte layer containing phosphorus from inside to outside. The composite positive electrode material is obtained by mixing and calcining lithium nickel cobalt manganese oxide coated by lithium niobate and sulfide solid electrolyte containing phosphorus. The composite positive electrode material provided by the disclosure can inhibit the interface reaction of the nickel cobalt lithium manganate and the sulfide solid electrolyte, ensure the stability of the structure and components of the nickel cobalt lithium manganate, increase the interface contact area of the positive electrode active material and the solid electrolyte, and improve the interface stability, so that the all-solid-state lithium battery assembled by adopting the composite positive electrode material has good multiplying power performance and cycle stability.
Description
Technical Field
The disclosure belongs to the technical field of lithium batteries, and particularly relates to a composite positive electrode material, a preparation method thereof and an all-solid-state lithium battery comprising the same.
Background
Lithium ion batteries have been widely used in a variety of fields including portable electronic products, electric vehicles, power grid storage, and the like. For electric vehicles with high endurance mileage in the future, higher energy density is required, and the energy density of commercial lithium ion batteries has reached a limit. In addition, leakage and thermal instability of highly flammable liquid electrolytes pose serious safety issues for commercial lithium ion batteries. To solve these problems, all-solid-state lithium battery technology has been widely recognized as one of the most promising candidate technologies.
Sulfide solid electrolyte having 10 -3 ～10 -2 S·cm -1 The lithium ion migration number close to 1 and good machinability, sulfide and active materials can easily form an electrolyte/electrolytic material interface with lower interface impedance only through a room temperature mechanical cold pressing process, and a communicated two-dimensional ion transmission channel is formed on the interface, so that the assembly preparation and the performance optimization of the all-solid-state battery are facilitated. The nickel cobalt lithium manganate positive electrode material has great advantages in energy density and cycle stability due to the synergistic effect of multiple metals. Combining sulfide solid electrolyte with nickel cobalt lithium manganate positive electrode active material to assemble all-solid-state battery will be a viable strategy to realize high performance all-solid-state battery.
However, the composite positive electrode material prepared by mixing the unmodified nickel cobalt lithium manganate positive electrode active material with the sulfide solid electrolyte can generate serious interface reaction in the battery cycle process, so that the interface impedance of the battery is increased sharply, further the exertion of the reversible specific capacity of the all-solid-state battery is limited, and the battery cycle stability is deteriorated. The composite positive electrode material prepared by mixing the coated nickel cobalt lithium manganate positive electrode active material and sulfide solid electrolyte has the advantages that the interfacial side reaction is relieved, but the poor solid-solid contact makes the ion transport blocked, and the rate performance of the assembled all-solid lithium battery is poor.
Therefore, how to prevent the interface reaction between the nickel cobalt lithium manganate positive electrode active material and the sulfide solid electrolyte and ensure the ion transmission of the interface between the nickel cobalt lithium manganate positive electrode active material and the sulfide solid electrolyte so as to improve the rate capability and the cycle stability of the lithium ion battery is a problem to be solved in the field.
Disclosure of Invention
In view of the shortcomings of the related art, an object of the present disclosure is to provide a composite positive electrode material, a method for preparing the same, and an all-solid-state lithium battery including the same. The composite positive electrode material can inhibit the interface reaction of nickel cobalt lithium manganate and sulfide solid electrolyte, ensure the stability of the structure and components of the nickel cobalt lithium manganate, increase the interface contact area and contact stability of the nickel cobalt lithium manganate and the sulfide solid electrolyte, and improve the ion transmission efficiency, so that the all-solid-state lithium battery prepared by adopting the composite positive electrode material has good cycle stability and multiplying power performance.
To achieve the purpose, the present disclosure adopts the following technical scheme:
in a first aspect, the present disclosure provides a composite positive electrode material that is a core-shell structure, comprising, in order from the inside to the outside, lithium nickel cobalt manganese oxide particles, a lithium niobate layer, a lithium phosphate layer, and a sulfide solid electrolyte layer containing phosphorus.
The composite positive electrode material with stable structure and components and high ion transmission efficiency is obtained through the matching of the lithium niobate layer, the lithium phosphate layer and the sulfide solid electrolyte layer containing phosphorus. Specifically, by forming the lithium phosphate protective layer between the lithium niobate layer and the sulfide solid electrolyte layer containing phosphorus, the interface reaction of the nickel cobalt lithium manganate and the sulfide solid electrolyte is restrained, the stability of the structure and components of the nickel cobalt lithium manganate is ensured, the solid electrolyte is uniformly coated outside the nickel cobalt lithium manganate, the interface contact area and contact stability of the positive electrode active material and the solid electrolyte are increased, and the ion transmission efficiency is improved, so that the all-solid lithium battery assembled by adopting the composite positive electrode material has good multiplying power performance and cycle stability.
In some embodiments of the present disclosure, the lithium nickel cobalt manganese oxide is selected from LiNi m Co n Mn 1-m-n O 2 One or more of the following;
where 0.5.ltoreq.m < 1 (e.g., may be 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, or 0.98, etc.), 0.5.ltoreq.m+n.ltoreq.1 (e.g., may be 0.5, 0.6, 0.7, 0.8, 0.9, or 1, etc.).
In some embodiments of the present disclosure, the sulfide solid electrolyte comprising phosphorus is selected from x (Li a G)·y(T c D d )·z(P 2 S 5 ) One or more of the following;
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, and z is more than or equal to 0 and less than 100;
a=1 or 2, c=1 or 2, d=1, 2 or 5;
the element G is S, cl, br or I;
the element T is Li, si, ge, P, sn or Sb;
element D is Cl, br, I, O, S or Se;
and Li is a G、T c D d And P 2 S 5 Different from each other, the metering numbers of Li, P and S are not 0.
In some embodiments of the present disclosure, the sulfide solid electrolyte comprising phosphorus is selected from the group consisting of Li 6-i P 1+j S 5-i Cl 1+i 、Li 6 PS 5 Cl、β-Li 3 PS 4 、Li 7 P 2 S 8 I and Li 6 PS 5 Cl 0.5 Br 0.5 One or more of the following; wherein i is more than or equal to 0.5 and less than or equal to 0.7,0, j is more than or equal to 0.5.
Wherein due to Li 6-i P 1+j S 5-i Cl 1+i The higher phosphorus content is more favorable for forming a lithium phosphate protective layer, so the sulfide solid electrolyte containing phosphorus in the present disclosure is more preferably Li 6-i P 1+j S 5-i Cl 1+i One or more of the following.
In a second aspect, the present disclosure provides a method for preparing the composite positive electrode material according to the first aspect, the method comprising the steps of:
and mixing and calcining lithium nickel cobalt manganese oxide coated by lithium niobate and a sulfide solid electrolyte containing phosphorus in a protective atmosphere to obtain the composite anode material.
The lithium niobate and the sulfide solid electrolyte containing phosphorus can react in situ to generate a lithium phosphate protective layer through calcination, so that the interface reaction of the nickel cobalt lithium manganate and the sulfide solid electrolyte can be inhibited, the stability of the structure and components of the nickel cobalt lithium manganate is ensured, the solid electrolyte can be uniformly coated outside the nickel cobalt lithium manganate, the interface contact area and contact stability of the positive electrode active material and the solid electrolyte are increased, and the ion transmission efficiency is improved.
In some embodiments of the disclosure, the protective atmosphere is an argon atmosphere or a nitrogen atmosphere.
In some embodiments of the present disclosure, the lithium niobate coated lithium nickel cobalt manganate has a content of lithium niobate of 0.05 to 5wt%; for example, 0.05wt%, 0.08wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.8wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt% may be used.
In some embodiments of the present disclosure, the mass ratio of the lithium niobate coated lithium nickel cobalt manganate to the sulfide solid electrolyte containing phosphorus is 70:30 to 80:20; for example, it may be 70:30, 72:28, 73:27, 75:25, 76:24, 78:22 or 80:20, etc. If the lithium niobate coated nickel cobalt lithium manganate is too small, the solid electrolyte of the sulfide containing phosphorus is too large, and the energy density of the battery is easy to be too low; if the lithium niobate coated nickel cobalt lithium manganate is too much, the coating effect is easily poor if the solid electrolyte of sulfide containing phosphorus is too little.
In some embodiments of the present disclosure, the temperature of the calcination is 400-600 ℃; for example, 400 ℃, 420 ℃, 450 ℃, 480 ℃,500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, or the like can be used.
In some embodiments of the present disclosure, the calcination time is 2-6 hours; for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, etc. may be used.
In some embodiments of the present disclosure, the calcination has a ramp rate of 1-10 ℃/min; for example, it may be 1℃per minute, 2℃per minute, 3℃per minute, 4℃per minute, 5℃per minute, 6℃per minute, 7℃per minute, 8℃per minute, 9℃per minute, 10℃per minute, or the like.
In some embodiments of the present disclosure, the method of preparing further comprises: after the calcination, the product was broken up.
In a third aspect, the present disclosure provides an all-solid lithium battery comprising the composite positive electrode material of the first aspect, a solid electrolyte, and a negative electrode material.
Compared with the related art, the method has the following beneficial effects:
the composite positive electrode material with stable structure and components and high ion transmission efficiency is obtained through the matching of the lithium niobate layer, the lithium phosphate layer and the sulfide solid electrolyte layer containing phosphorus. Specifically, by forming the lithium phosphate protective layer between the lithium niobate layer and the sulfide solid electrolyte layer containing phosphorus, the interface reaction of the nickel cobalt lithium manganate and the sulfide solid electrolyte is restrained, the stability of the structure and components of the nickel cobalt lithium manganate is ensured, the solid electrolyte is uniformly coated outside the nickel cobalt lithium manganate, the interface contact area and contact stability of the positive electrode active material and the solid electrolyte are increased, and the ion transmission efficiency is improved, so that the all-solid lithium battery assembled by adopting the composite positive electrode material has good multiplying power performance and cycle stability.
Drawings
FIG. 1 is an X-ray diffraction chart of the composite positive electrode material provided in example 1;
FIG. 2 is an X-ray diffraction chart of the composite positive electrode material provided in comparative example 1;
FIG. 3 is an X-ray diffraction pattern of the composite positive electrode material provided in comparative example 2;
fig. 4 is a graph of the rate performance of an all-solid lithium battery employing the composite cathode material provided in example 1;
fig. 5 is a cycle performance graph of an all-solid-state lithium battery employing the composite cathode material provided in example 1;
fig. 6 is a graph of the rate performance of an all-solid lithium battery employing the composite cathode material provided in comparative example 1;
fig. 7 is a cycle performance graph of an all-solid lithium battery employing the composite cathode material provided in comparative example 1.
Detailed Description
The technical scheme of the present disclosure is further described below by means of specific embodiments in combination with the accompanying drawings. It should be apparent to those skilled in the art that the detailed description is merely provided for the purpose of facilitating an understanding of the disclosure and should not be taken as limiting the disclosure in any way.
Example 1
The embodiment provides a composite positive electrode material which has a core-shell structure and sequentially comprises LiNi from inside to outside 0.6 Co 0.2 Mn 0.2 O 2 Particles, lithium niobate layers, lithium phosphate layers, and Li 5.4 P 1.1 S 4.4 Cl 1.6 Sulfide solid electrolyte layer.
The preparation method of the composite positive electrode material comprises the following steps:
weighing lithium niobate coated LiNi according to the mass ratio of 70:30 0.6 Co 0.2 Mn 0.2 O 2 Positive electrode active material (containing lithium niobate 0.05 wt%) and Li 5.4 P 1.1 S 4.4 Cl 1.6 The sulfide solid electrolyte is manually ground and mixed for 30 minutes, the heating rate is controlled to be 2 ℃/min in an argon atmosphere, the mixture is sintered for 4 hours at 400 ℃, and the product is scattered, so that the composite anode material (D50 particle size is 50 microns) is obtained.
Example 2
The embodiment provides a composite positive electrode material which has a core-shell structure and sequentially comprises LiNi from inside to outside 0.6 Co 0.2 Mn 0.2 O 2 Particles, lithium niobate layers, lithium phosphate layers, and Li 5.5 P 1.2 S 4.5 Cl 1.5 Sulfide solid electrolyte layer.
The preparation method of the composite positive electrode material comprises the following steps:
weighing LiNi coated by lithium niobate according to the mass ratio of 72:28 0.5 Co 0.3 Mn 0.2 O 2 Positive electrode active material (containing 0.1wt% of lithium niobate) and Li 5.5 P 1.2 S 4.5 Cl 1.5 The sulfide solid electrolyte is mixed for 50 minutes by a roller mill at 300 revolutions per minute, the heating rate is controlled to be 9 ℃/min in an argon atmosphere, the mixture is sintered for 6 hours at 450 ℃, and the product is scattered, so that the composite anode material (D50 particle size is 30 microns) is obtained.
Example 3
The embodiment provides a composite positive electrode material which has a core-shell structure and sequentially comprises LiNi from inside to outside 0.8 Co 0.1 Mn 0.1 O 2 Particles, lithium niobate layers, lithium phosphate layers, and Li 5.3 P 1.3 S 4.3 Cl 1.7 Sulfide solid electrolyte layer.
The preparation method of the composite positive electrode material comprises the following steps:
weighing lithium niobate coated LiNi according to the mass ratio of 75:25 0.8 Co 0.1 Mn 0.1 O 2 Positive electrode active material (containing 0.2wt% of lithium niobate) and Li 5.3 P 1.3 S 4.3 Cl 1.7 The sulfide solid electrolyte is ball-milled and mixed for 20 minutes at 300 r/min, the heating rate is controlled to be 5 ℃ per minute in nitrogen atmosphere, the mixture is sintered for 3 hours at 500 ℃, and the product is scattered, so that the composite anode material (D50 particle size is 10 microns) is obtained.
Example 4
The embodiment provides a composite positive electrode material which has a core-shell structure and sequentially comprises LiNi from inside to outside 0.9 Mn 0.1 O 2 Particles, lithium niobate layers, lithium phosphate layers, and Li 5.4 P 1.1 S 4.4 Cl 1.6 Sulfide solid electrolyte layer.
The preparation method of the composite positive electrode material comprises the following steps:
weighing LiNi coated by lithium niobate according to the mass ratio of 78:22 0.9 Mn 0.1 O 2 Positive electrode active material (containing lithium niobate 2 wt%) and Li 5.4 P 1.1 S 4.4 Cl 1.6 Sulfide solid electrolyte, 500 times/min shaking mixing for 45 minutes, and controlling the temperature rising rate to be 10 ℃ in nitrogen atmosphereAnd (3) min, sintering at 550 ℃ for 5 hours, and scattering the product to obtain the composite positive electrode material (D50 particle size is 5 microns).
Example 5
The embodiment provides a composite positive electrode material which has a core-shell structure and sequentially comprises LiNi from inside to outside 0.98 Mn 0.02 O 2 Particles, lithium niobate layers, lithium phosphate layers, and Li 5.4 P 1.1 S 4.4 Cl 1.6 Sulfide solid electrolyte layer.
The preparation method of the composite positive electrode material comprises the following steps:
weighing lithium niobate coated LiNi according to the mass ratio of 80:20 0.98 Mn 0.02 O 2 Positive electrode active material (containing 5wt% of lithium niobate) and Li 5.4 P 1.1 S 4.4 Cl 1.6 The sulfide solid electrolyte is manually ground and mixed for 1 hour, the heating rate is controlled to be 1 ℃/min in a nitrogen atmosphere, the mixture is sintered for 2 hours at 600 ℃, and the product is scattered, so that the composite anode material (D50 particle size is 2 microns) is obtained.
Example 6
This example provides a composite positive electrode material, the preparation method of which differs from example 3 only in that Li is 5.3 P 1.3 S 4.3 Cl 1.7 Replacement of sulfide solid electrolyte with beta-Li 3 PS 4 。
Example 7
This example provides a composite positive electrode material, the preparation method of which differs from example 3 only in that Li is 5.3 P 1.3 S 4.3 Cl 1.7 Replacement of sulfide solid electrolyte with Li 7 P 2 S 8 I。
Comparative example 1
This comparative example provides a composite positive electrode material, which is prepared by a method differing from example 1 only in that the composite positive electrode material is directly obtained without performing a sintering operation after mixing by manual grinding for 30 minutes.
Comparative example 2
This comparative example provides a composite positive electrode material, the preparation method of which differs from example 1 only in that lithium niobate is coatedLiNi of (C) 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode active material (containing 0.05wt% of lithium niobate) was replaced with lithium lanthanum zirconium oxide (Li) 7 La 3 Zr 2 O 12 LLZO) coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Positive electrode active material (lithium-containing lanthanum zirconium oxygen 0.05 wt%).
Comparative example 3
This comparative example provides a composite positive electrode material, the preparation method of which differs from example 1 only in that lithium niobate is coated with LiNi 0.6 Co 0.2 Mn 0.2 O 2 Replacement of positive electrode active material (containing lithium niobate 0.05 wt%) with lithium phosphate coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Positive electrode active material (containing lithium phosphate 0.05 wt%).
Characterization by X-ray diffraction:
the composite positive electrode materials provided in example 1, comparative example 1 and comparative example 2 were characterized using an X-ray diffractometer, and the results are shown in fig. 1, fig. 2 and fig. 3, respectively.
As can be seen from fig. 1, lithium phosphate was generated in the composite cathode material provided in example 1; as can be seen from fig. 2, in comparative example 1, since sintering was not performed, lithium niobate and sulfide solid electrolyte were not reacted, and lithium phosphate was not generated; as can be seen from fig. 3, lithium lanthanum zirconium oxide in comparative example 2 did not react with sulfide solid electrolyte to produce lithium phosphate.
Electrochemical performance test:
the composite positive electrode materials provided in the above examples and comparative examples were pressed at a pressure of 180MPa in Li 6 PS 5 The Cl solid electrolyte layer is coated to obtain a positive plate with a composite positive material layer tightly combined with the electrolyte layer; pressing a current collector on the composite positive electrode material layer of the positive electrode plate; and placing a lithium indium alloy layer and a current collector on the other side of the electrolyte layer in sequence, and then pressing to obtain the all-solid-state lithium battery.
The initial charge and discharge efficiency (0.1C), the rate performance of 0.1 to 1C and the charge and discharge cycle performance at 1C of the all-solid-state lithium battery under the conditions of charge and discharge voltage of 2.4V to 3.7V, pressure of 90MPa and room temperature were tested, and the results are shown in the following tables 1 and 2.
TABLE 1
TABLE 2
The rate performance and cycle performance of an all-solid lithium battery using the composite cathode material provided in example 1 are shown in fig. 4 and 5, respectively. The rate performance and cycle performance of an all-solid lithium battery using the composite cathode material provided in comparative example 1 are shown in fig. 6 and 7, respectively. In fig. 4 and 5, the 2 nd to 6 th turns have a magnification of 0.1C, the 7 th to 11 th turns have a magnification of 0.2C, the 12 th to 16 th turns have a magnification of 0.3C, and the 17 th to 21 th turns have a magnification of 1C.
As can be seen from the experimental results of tables 1 and 2 and fig. 4 to 7, the all-solid-state lithium battery using the composite material provided by the present disclosure has good rate performance and cycle performance. Compared with example 1, comparative example 1 was not sintered, and comparative example 2 was not provided with a lithium phosphate protective layer because lithium lanthanum zirconium oxygen coated nickel cobalt lithium manganate was used instead of lithium niobate coated nickel cobalt lithium manganate, resulting in a significant decrease in the rate performance and cycle performance of all solid-state lithium batteries using the same. Comparative example 3, although lithium phosphate-coated lithium nickel cobalt manganese oxide was directly used, the contact between the electrolyte layer and the active material was poor, resulting in poor rate performance and cycle performance of the all-solid lithium battery assembled therewith.
The foregoing is merely a specific embodiment of the disclosure to enable one skilled in the art to understand or practice the disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The composite positive electrode material is characterized by being of a core-shell structure and sequentially comprising nickel cobalt lithium manganate particles, a lithium niobate layer, a lithium phosphate layer and a sulfide solid electrolyte layer containing phosphorus from inside to outside.
2. The composite positive electrode material according to claim 1, wherein the lithium nickel cobalt manganate is selected from LiNi m Co n Mn 1-m-n O 2 One or more of the following;
wherein m is more than or equal to 0.5 and less than 1, and m+n is more than or equal to 0.5 and less than or equal to 1.
3. The composite positive electrode material according to claim 1 or 2, wherein the sulfide solid electrolyte containing phosphorus is selected from x (Li a G)·y(T c D d )·z(P 2 S 5 ) One or more of the following;
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, and z is more than or equal to 0 and less than 100;
a=1 or 2, c=1 or 2, d=1, 2 or 5;
the element G is S, cl, br or I;
the element T is Li, si, ge, P, sn or Sb;
element D is Cl, br, I, O, S or Se;
and Li is a G、T c D d And P 2 S 5 Different from each other, the metering numbers of Li, P and S are not 0.
4. The composite positive electrode material according to any one of claims 1 to 3, wherein the electrode material containsThe sulfide solid electrolyte of phosphorus is selected from Li 6-i P 1+j S 5-i Cl 1+i 、Li 6 PS 5 Cl、β-Li 3 PS 4 、Li 7 P 2 S 8 I and Li 6 PS 5 One or more of ClBr; wherein i is more than or equal to 0.5 and less than or equal to 0.7,0, j is more than or equal to 0.5;
preferably, the sulfide solid electrolyte containing phosphorus is selected from Li 6-i P 1+j S 5-i Cl 1+i One or more of the following.
5. A method of preparing the composite positive electrode material according to any one of claims 1 to 4, comprising the steps of:
and mixing and calcining lithium nickel cobalt manganese oxide coated by lithium niobate and a sulfide solid electrolyte containing phosphorus in a protective atmosphere to obtain the composite anode material.
6. The method according to claim 5, wherein the protective atmosphere is an argon atmosphere or a nitrogen atmosphere.
7. The method according to claim 5 or 6, wherein the lithium niobate coated lithium nickel cobalt manganate has a content of 0.05 to 5wt%;
preferably, the mass ratio of the lithium niobate coated lithium nickel cobalt manganate to the sulfide solid electrolyte containing phosphorus is 70:30-80:20.
8. The method of any one of claims 5-7, wherein the calcination temperature is 400-600 ℃;
preferably, the calcination time is 2-6 hours;
preferably, the temperature rising rate of the calcination is 1-10 ℃/min.
9. The method of any one of claims 5-8, further comprising: after the calcination, the product was broken up.
10. An all-solid-state lithium battery comprising the composite positive electrode material of any one of claims 1 to 4, a solid electrolyte, and a negative electrode material.
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