CN114843616A - Lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility and preparation method thereof - Google Patents
Lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility and preparation method thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011572 manganese Substances 0.000 title claims abstract description 53
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- 239000002134 carbon nanofiber Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 229910000846 In alloy Inorganic materials 0.000 claims description 8
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910008323 Li-P-S Inorganic materials 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 229910006736 Li—P—S Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000010416 ion conductor Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 17
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007600 charging Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 3
- 229910002982 Li2MnO3 phase Inorganic materials 0.000 description 3
- 229910003005 LiNiO2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a preparation method of a lithium-rich manganese-based all-solid-state lithium ion battery with high interface compatibility. The solid-state lithium ion battery comprises a lithium-manganese-rich positive electrode material, a sulfide solid-state electrolyte and a negative electrode material. The invention relates to 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 ‑0.6Li 2 MnO 3 ‑0.1LiNiO 2 The lithium-rich manganese cathode material is applied to an all-solid-state lithium ion battery by means of Li 2 MnO 3 The interface decomposition reaction energy with sulfide solid electrolyte is small, and the LPSCl electrolyte can play a role in S aiming at the special anion redox mechanism of the lithium-manganese-rich positive electrode 2‑ /SO 3 2‑ The effect of redox couple is to generate O in time during charging 2 2‑ The ions are reduced, thereby inhibiting the release of oxygen from the lithium manganese rich positive electrode. The highest first discharge specific capacity of the all-solid-state battery under the current density of 0.5C can reach 167.2mAh g ‑1 And after the lithium ion battery is cycled for 1000 circles under the current density of 0.5C, the high capacity retention rate can be still maintained, excellent cycle stability is shown, and the energy density of the all-solid-state lithium ion battery is improved.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility and a preparation method thereof.
Background
In recent years, safety accidents of new energy electric automobiles are frequent, and part of the reason is that the safety performance of lithium ion batteries using flammable liquid organic carbonate electrolytes is reduced while the energy density is improved. The all-solid-state lithium battery uses a solid electrolyte which is not easy to burn, and can give consideration to the characteristics of high energy density and high safety of the battery. In addition, the solid electrolyte with high oxidation potential can reduce the side reaction of the high-voltage positive electrode interface, so that the performance of the solid electrolyte is more stable. At present, research on all-solid-state lithium batteries has become an inevitable trend in the development of lithium ion batteries. The development of high-specific-energy all-solid-state lithium batteries with high safety is a development trend, and the selection of positive and negative electrode materials with high specific capacity is the key for manufacturing the high-specific-energy all-solid-state lithium batteries. At present, lithium-rich manganese-based materials have ultrahigh specific capacity (> 250 mAh. g) due to the lithium-rich manganese-based materials -1 ) Low cost and high safety, and is concerned by scientists and engineers in all countries around the world.
However, there is currently a fresh research on the application of lithium-rich manganese base in solid-state lithium ion batteries. It is well known that the ionic conductivity of sulfide electrolytes has now reached a high level, the ionic conductivity of electrolytes is no longer a short plate of all-solid batteries, and various interface problems in all-solid batteries are the main factors limiting the performance of all-solid batteries. On the positive electrode side, for LiCoO 2 And the research on high-nickel cathode materials shows that the oxide cathodes and the sulfide electrolytes are thermodynamically unstable when in contact, have larger interfacial decomposition reaction energy, and can generate serious interfacial side reaction in the circulating process, thereby causing the deterioration of the performance of the sulfide all-solid-state battery. However, the interface problem between the lithium-manganese-rich cathode material and the sulfide electrolyte is not studied at present.
Disclosure of Invention
In order to solve the problems, the invention provides a lithium-rich manganese-based all-solid-state lithium ion battery with high interface compatibility and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme provided by the invention is as follows:
a preparation method of a lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility comprises the following steps:
1) mixing a lithium-rich manganese active material, sulfide solid electrolyte powder and a conductive agent according to the mass part ratio of 30-90: 20-45: 3-7, fully mixing and grinding to obtain the lithium-manganese-rich positive electrode material, wherein the lithium-manganese-rich active material (1-x) LiNi 0.33 Co 0.43 Mn 0.23 O 2 -xLi 2 MnO 3 -yLiNiO 2 X is more than 0 and less than 1, and y is more than or equal to 0 and less than or equal to 0.7;
2) adding sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1-2min at the pressure of 400-600MPa to press the powder electrolyte into a raw sheet;
3) uniformly scattering a lithium-manganese-rich positive electrode material on one side of the electrolyte raw sheet, and maintaining the pressure for 2-4min at the pressure of 400-600 MPa;
4) and adding a lithium indium alloy sheet on the other side of the electrolyte raw sheet.
In the total mass of the battery, the lithium-rich manganese anode material is 30-90 parts, the sulfide solid electrolyte is 20-45 parts, and the conductive agent is 3-7 parts.
The lithium-manganese-rich positive electrode material accounts for 40-70 parts of the total mass of the battery.
The sulfide solid electrolyte is Li-P-S-based electrolyte or Li 6 PS 5 Cl-AgGeranite and sulfide crystal lithium super ion conductor.
The conductive agent is one or a mixture of more than two of carbon black, carbon nano tubes, acetylene black, VGCF, Super P, conductive graphite and carbon fibers.
The sulfide solid electrolyte is preferably Li 6 PS 5 Cl, the conductive agent is preferably VGCF.
In the lithium-rich manganese active material, x is 0.55 or 0.6, and y is 0,0.03,0.05,0.07 or 0.10.
The lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention develops a positive electrode material which takes a lithium-rich manganese active material as a main material and takes a sulfide solid electrolyte and a conductive agent as auxiliary materials. The lithium-rich manganese active material has high interface compatibility with sulfide solid electrolyte, and Li in the lithium-rich manganese active material is adjusted 2 MnO 3 In an amount to improve interface compatibility, Li 2 MnO 3 The higher the content is, the smaller the interface side reaction is, and the smaller the interface side reaction is beneficial to reducing the interface impedance of the all-solid-state battery.
2. Aiming at the special anion redox mechanism of the lithium-manganese-rich positive electrode, the sulfide solid electrolyte can play the role of S 2- /SO 3 2- The effect of redox couple is to generate O in time during charging 2 2- And ions are reduced, so that the oxygen release of the lithium-manganese-rich anode is inhibited, and the structural integrity and the cycling stability of the lithium-manganese-rich anode in the cycling process are ensured. The highest discharge capacity under 0.1C can reach 242.5mAh g -1 The capacity does not fade after being cycled for 100 times at 0.1 ℃, the capacity retention rate is 100%, and the capacity retention rate is up to 87% after being cycled for 1000 times at 0.5 ℃, so that the excellent cycling stability is shown.
3. The lithium ion battery prepared by the preparation method provided by the invention has excellent interface compatibility, and shows that the lithium-manganese-rich anode with high manganese content and Li 6 PS 5 The interface decomposition reaction of the Cl electrolyte is small, and the lithium-rich manganese all-solid-state lithium ion battery with higher discharge capacity and better cycle performance is obtained.
4. The lithium-manganese-rich material can be prepared by a one-step method, has simple and efficient process, and is expected to realize the full solid application of the high-capacity lithium-manganese-rich material.
Drawings
FIG. 1 is an X-ray diffraction pattern of the positive electrode material prepared in example 1;
fig. 2 is a 0.5C cycle performance curve for the assembled cell of example 1;
FIG. 3 is an X-ray diffraction pattern of the cathode material prepared in example 2;
fig. 4 is a 0.5C cycle performance curve for an assembled cell of example 2;
FIG. 5 is an X-ray diffraction pattern of the positive electrode material prepared in comparative example 1;
fig. 6 is a 0.5C cycle performance curve for an assembled cell of comparative example 1;
FIG. 7 is an X-ray diffraction pattern of the positive electrode material prepared in comparative example 2;
fig. 8 is a 0.5C cycle performance curve for an assembled cell of comparative example 2;
fig. 9 is a 0.5C cycle performance curve for an assembled cell of example 3;
fig. 10 is a 0.5C cycle performance curve for an assembled cell of example 4;
fig. 11 is a 0.5C cycle performance curve for an assembled cell of example 5;
fig. 12 is a 0.5C cycle performance curve for the assembled cell of example 6.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
a preparation method of a lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility comprises the following steps:
1) mixing lithium-rich manganese active material 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 Solid electrolyte powder of sulfide Li 6 PS 5 And (3) Cl and a conductive agent VGCF are fully mixed and ground manually according to the mass ratio of 60:35:5 to obtain the lithium-manganese-rich cathode material.
2) Mixing sulfide solid electrolyte powder Li 6 PS 5 And adding Cl into a tabletting mold, and keeping the pressure for 1min at the pressure of 510MPa to press the powdery electrolyte into the original tablet.
3) And uniformly scattering a lithium-manganese-rich positive electrode material on one side of the electrolyte raw sheet, and maintaining the pressure at 510MPa for 3 min.
4) And adding a lithium indium alloy sheet with the thickness of 0.1mm on the other side of the electrolyte raw sheet.
The test voltage window is 2.0-4.8V (Li/Li) + ) And testing the electrochemical performance of the battery by adopting a constant current charging and discharging mode.
According to the XRD pattern (figure 1), the synthesized sample is a typical lithium-rich manganese structure and belongs to alpha-NaFeO 2 A layer-shaped structure. In which the small peak in the range of 20-24 corresponds to Li 2 MnO 3 A superstructure of phases. 105.3mAh g still remained after 700 cycles -1 Capacity (fig. 2).
Example 2:
the preparation process is essentially the same as in example 1, except that:
0.45LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.55Li 2 MnO 3 A lithium-manganese rich cathode material.
As can be seen from the XRD pattern (FIG. 3), the synthesized sample is also a typical lithium-rich manganese structure belonging to alpha-NaFeO 2 A layer-shaped structure. In which the small peak in the range of 20-24 corresponds to Li 2 MnO 3 The superstructure of the phase, only the intensity of the peaks being different, represents different contents of Li 2 MnO 3 Phase, 98.39mAh g after 700 cycles -1 Capacity (fig. 4).
Comparative example 1:
the preparation process is essentially the same as in example 1, except that:
0.35LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.65Li 2 MnO 3 A lithium-manganese rich cathode material.
According to the XRD pattern (figure 5), the synthesized sample is also a typical lithium-rich manganese structure and belongs to alpha-NaFeO 2 And a layer-shaped structure. In which the small peak in the range of 20-24 corresponds to Li 2 MnO 3 The superstructure of the phase, only the intensity of the peaks being different, represents different contents of Li 2 MnO 3 Phase, after 700 cycles, only 6.42mAh g -1 Capacity (fig. 6).
Comparative example 2:
1) 0.3LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.7Li 2 MnO 3 The lithium-manganese-rich cathode material, the sulfide solid electrolyte and the VGCF are fully mixed according to the mass ratio of 60:35:5 to obtain a mixture.
2) And adding the sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1min at the pressure of 510MPa to form the electrolyte.
3) Next, 0.3LiNi was uniformly spread on one side of the sulfide solid electrolyte sheet 0.33 Co 0.43 Mn 0.23 O 2 -0.7Li 2 MnO 3 And (3) the lithium-manganese-rich cathode material is subjected to pressure maintaining for 3min at the pressure of 510 MPa. Then, a lithium indium alloy sheet was attached to the mold. The test voltage window is 2.0-4.8V (Li/Li) + ) And testing the electrochemical performance of the battery by adopting a constant current charging and discharging mode.
According to the XRD pattern (figure 7), the synthesized sample is also a typical lithium-rich manganese structure and belongs to alpha-NaFeO 2 A layer-shaped structure. In which the small peak in the range of 20-24 corresponds to Li 2 MnO 3 The superstructure of the phase, only the intensity of the peaks being different, represents different contents of Li 2 MnO 3 Phase, after 700 cycles, only 6.25mAh g -1 Capacity (fig. 8).
Example 3:
1) 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.1LiNiO 2 The lithium-manganese-rich cathode material, the sulfide solid electrolyte and the VGCF are fully mixed according to the mass ratio of 60:35:5 to obtain a mixture.
2) And adding the sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1min at the pressure of 510MPa to form the electrolyte.
3) Next, 0.4LiNi was uniformly spread on one side of the sulfide solid electrolyte sheet 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.1LiNiO 2 And (3) the lithium-manganese-rich cathode material is subjected to pressure maintaining for 3min at the pressure of 510 MPa. Then, a lithium indium alloy sheet was attached to the mold. The test voltage window is 2.0-4.8V (Li/Li) + ) The electrochemical performance of the battery is carried out by adopting a constant current charging and discharging modeCan be tested.
The first discharge capacity at a current density of 0.5C was 167.2mAh g -1 After 1000 cycles, the capacity is 145.5mAh g -1 The capacity retention rate was 87% (fig. 9).
Example 4:
1) 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.03LiNiO 2 The lithium-manganese-rich cathode material, the sulfide solid electrolyte and the VGCF are fully mixed according to the mass ratio of 60:35:5 to obtain a mixture.
2) And adding the sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1min at the pressure of 510MPa to form the electrolyte.
3) Next, 0.4LiNi was uniformly spread on one side of the sulfide solid electrolyte sheet 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.03LiNiO 2 And (3) the lithium-manganese-rich cathode material is subjected to pressure maintaining for 3min at the pressure of 510 MPa. Then, a lithium indium alloy sheet was attached to the mold. The test voltage window is 2.0-4.8V (Li/Li) + ) And testing the electrochemical performance of the battery by adopting a constant current charging and discharging mode.
The first discharge capacity at a current density of 0.5C was 199.7mAh g -1 After 700 cycles, the capacity is 139.2mAh g -1 The capacity retention rate was 69.7% (fig. 10).
Example 5
1) 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.05LiNiO 2 The lithium-manganese-rich cathode material, the sulfide solid electrolyte and the VGCF are fully mixed according to the mass ratio of 60:35:5 to obtain a mixture.
2) And adding the sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1min at the pressure of 510MPa to form the electrolyte.
3) Next, 0.4LiNi was uniformly spread on one side of the sulfide solid electrolyte sheet 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.05LiNiO 2 And (3) the lithium-manganese-rich cathode material is subjected to pressure maintaining for 3min at the pressure of 510 MPa. Then, a lithium indium alloy sheet was attached to the mold. The test voltage window is 2.0-4.8V (Li/Li) + ) And testing the electrochemical performance of the battery by adopting a constant current charging and discharging mode.
The first discharge capacity at a current density of 0.5C was 200.9mAh g -1 After 1000 cycles, the capacity is 147.2mAh g -1 The capacity retention ratio was 73.3% (fig. 11).
Example 6
1) 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.07LiNiO 2 The lithium-manganese-rich cathode material, the sulfide solid electrolyte and the VGCF are fully mixed according to the mass ratio of 60:35:5 to obtain a mixture.
2) And adding the sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1min at the pressure of 510MPa to form the electrolyte.
3) Next, 0.4LiNi was uniformly spread on one side of the sulfide solid electrolyte sheet 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -0.07LiNiO 2 And (3) the lithium-manganese-rich cathode material is subjected to pressure maintaining for 3min at the pressure of 510 MPa. Then, a lithium indium alloy sheet was attached to the mold. The test voltage window is 2.0-4.8V (Li/Li) + ) And testing the electrochemical performance of the battery by adopting a constant current charging and discharging mode.
The first discharge capacity at a current density of 0.5C was 182.1mAh g -1 After 1000 cycles, the capacity is 145.3mAh g -1 The capacity retention ratio was 79.8% (fig. 12).
The above specific examples were analyzed as follows:
(1) lithium-rich manganese oxide positive electrode and Li 6 PS 5 Cl sulfide electrolytes have high interfacial compatibility, which is manifested in two ways. On the one hand, compared with the traditional lithium cobaltate and high nickel positive electrode, the lithium-manganese-rich positive electrode with high manganese content and Li 6 PS 5 The interfacial decomposition reaction energy of Cl is small, and the higher the Li2MnO3 content is, the interface isThe smaller the side reaction is, the smaller the interface side reaction is beneficial to the reduction of the interface impedance of the sulfide all-solid-state battery; on the other hand, Li is a specific anion redox mechanism for lithium manganese rich positive electrodes 6 PS 5 The Cl electrolyte can play a role of an S2-/SO 32-redox couple, and timely reduces generated O22-ions in the charging process, SO that oxygen release of the lithium-manganese-rich anode is inhibited, and the structural integrity and the cycling stability of the lithium-manganese-rich anode in the cycling process are ensured.
(2) Increasing the Li2MnO3 content of the Li-rich manganese positive electrode increases Li and Mn 6 PS 5 The interface compatibility of Cl, but at the same time, the electronic and ionic conductivity of the material is also reduced, which is not favorable for the expression of electrochemical performance. Wherein, the 0.6LMO anode has moderate electronic and ionic conductivity (3.27 multiplied by 10 < -7 > and 3.95 multiplied by 10 < -8 > S cm < -1 > respectively), and the all-solid-state battery has high discharge capacity of 258mAh g < -1 > at 0.1 ℃, and the capacity retention rate can reach 77.4 percent after 100 cycles. However, at a higher current density, the conductivity is not favorable for the expression of electrochemical performance, and the capacity retention rate is only 49% after the electrochemical device is cycled for 700 times at 0.5 ℃.
(3) Increasing the content of the LiNiO2 component in the lithium-manganese-rich positive electrode can significantly improve the electronic and ionic conductivity of the lithium-manganese-rich positive electrode. Meanwhile, the additionally introduced Ni ions in the LiNiO2 component selectively occupy lithium sites in the Li2MnO3(C2/m) phase instead of LiTMO2(R '3') "
) Lithium sites in phase, 0.4LiNi complexed with LiNiO2 component 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -yLiNiO 2 The lithium-manganese rich positive electrode and the LPSCl electrolyte still have high interface compatibility, so that 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -yLiNiO 2 The positive electrode shows better electrochemical performance in the sulfide all-solid-state battery. Wherein the maximum discharge capacity of the anode in the embodiment 5 under 0.1C can reach 255.8mAh g-1, the energy density can reach 874Wh kg-1, the capacity retention rate after the anode is circulated for 100 times under 0.1C can reach 93.5 percent, and the capacity retention rate can reach 0.5 percentThe capacity retention rate can reach 73.3 percent after the circulation for 1000 times under C. The highest discharge capacity of the 0.6LMO @10LN positive electrode at 0.1C can reach 242.5mAh g-1, the capacity is not attenuated after the circulation for 100 times at 0.1C, the capacity retention rate is 100 percent, and the assembled 0.4LiNi 0.33 Co 0.43 Mn 0.23 O 2 -0.6Li 2 MnO 3 -yLiNiO 2 The all-solid-state battery has higher discharge capacity and better cycle stability than the LRCo10@ yLN all-solid-state battery.
The conclusion reached is: example 3 is the most preferred example.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A preparation method of a lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility comprises the following steps:
1) mixing a lithium-rich manganese active material, sulfide solid electrolyte powder and a conductive agent according to the mass part ratio of 30-90: 20-45: 3-7, fully mixing and grinding to obtain the lithium-manganese-rich positive electrode material, wherein the lithium-manganese-rich active material (1-x) LiNi 0.33 Co 0.43 Mn 0.23 O 2 -xLi 2 MnO 3 -yLiNiO 2 X is more than 0 and less than 1, and y is more than or equal to 0 and less than or equal to 0.7;
2) adding sulfide solid electrolyte powder into a tabletting mold, and maintaining the pressure for 1-2min at the pressure of 400-600MPa to press the powder electrolyte into a wafer;
3) uniformly scattering a lithium-manganese-rich positive electrode material on one side of the electrolyte wafer, and maintaining the pressure for 2-4min at the pressure of 400-600 MPa;
4) a piece of lithium indium alloy was added to the other side of the electrolyte wafer.
2. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 1, wherein: in the total mass of the battery, the lithium-rich manganese anode material is 30-90 parts, the sulfide solid electrolyte is 20-45 parts, and the conductive agent is 3-7 parts.
3. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 2, wherein: the lithium-manganese-rich positive electrode material accounts for 40-70 parts of the total mass of the battery.
4. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 3, wherein: the sulfide solid electrolyte is Li-P-S-based electrolyte or Li 6 PS 5 Cl-AgGeranite and sulfide crystal lithium super ion conductor.
5. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 3, wherein: the conductive agent is one or a mixture of more than two of carbon black, carbon nano tubes, acetylene black, VGCF, Super P, conductive graphite and carbon fibers.
6. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 4 or 5, wherein: the sulfide solid electrolyte is preferably Li 6 PS 5 Cl, the conductive agent is preferably VGCF.
7. The method for preparing a lithium-rich manganese-based all-solid-state lithium battery with high interfacial compatibility according to claim 6, wherein: in the lithium-manganese-rich active material, x is 0.55 or 0.6, and y is 0,0.03,0.05,0.07 or 0.10.
8. The lithium-rich manganese-based all-solid-state lithium battery with high interface compatibility prepared by the preparation method of claim 1.
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