Heteroanion oxyhalide solid-state electrolyte, preparation method, application and full solid-state battery thereof

Abstract

The application discloses a kind of miscellaneous anion oxyhalide solid electrolyte and preparation method, application and full solid battery thereof;Belong to solid battery technical field.The electrolyte material chemical formula is Li （3d+2e+2f+g） M m+ b N n+ c (PO4) d (SO4) e (CO3) f (OH) g X (mb+nc) , M is alkaline earth metal, N is one or more of transition metal, rare earth metal and P area metal, X is at least one of F, Cl, Br and I.The twisted Li-X sublattice structure formed by introducing halogen atom of the material of the application significantly reduces lithium ion migration barrier, expands lithium ion transport channel through special angle sharing oxygen network structure, also endows material with excellent mechanical flexibility, and the halogen-rich passivation layer spontaneously formed on the surface of the material makes it show excellent environmental stability;Not only solve the key material bottleneck of solid battery development, more provide solid technical support for promoting new energy industry to higher safety, higher energy density direction development.

Description

Technical Field

[0001] This invention belongs to the field of solid-state battery technology, specifically relating to a heteroanion oxyhalide solid electrolyte, its preparation method, application, and all-solid-state battery. Background Technology

[0002] With the accelerated global energy transition and electrification, the new energy industry is placing dual demands on energy storage devices for higher energy density and greater safety. Traditional liquid lithium-ion batteries, limited by their organic electrolyte systems, have energy densities nearing their theoretical limits (generally below 200 Wh / kg) and pose serious safety hazards, making them unsuitable for the stringent requirements of high-end applications such as electric vehicles, smart grids, and aerospace. Against this backdrop, all-solid-state batteries, employing solid-state electrolytes and lithium metal anodes, are considered a revolutionary solution for next-generation energy storage technology due to their theoretical energy density exceeding 500 Wh / kg and the complete elimination of electrolyte combustion risks.

[0003] Solid-state electrolytes are the core component of all-solid-state batteries, and their performance directly determines the overall performance of the battery. Current mainstream research focuses on three main technical routes: oxide solid-state electrolytes (OSEs), while possessing excellent chemical stability, generally have low room-temperature ionic conductivity (approximately 10⁻⁶). -4 S / cm), and the excessively high mechanical modulus leads to poor electrode / electrolyte interface contact; sulfide solid electrolytes (SSE), although exhibiting extremely high ionic conductivity (up to 10 S / cm), also exhibit poor electrode / electrolyte interface contact. - ² S / cm), but suffers from severe air sensitivity, a narrow electrochemical window (1.7-2.5V), and high manufacturing costs; halide solid electrolytes (HSE), while to some extent balancing ionic conductivity (10 S / cm), also have other drawbacks. - ³-10 - While achieving high performance in solid-state batteries (withstanding voltage >4V) and electrochemical stability (s / cm²), they still face significant hydrolytic failure issues. These technological bottlenecks severely restrict the commercialization of all-solid-state batteries.

[0004] This material employs an innovative "metal-heteroanion-halogen synergistic doping" strategy to design a flexible anionic framework structure at the molecular level. Its breakthrough lies in: effectively reducing the activation energy of lithium-ion migration by introducing divalent alkaline earth metal ions to anchor and stabilize the anionic framework; simultaneously, the addition of halogen atoms forms a distorted Li-X sublattice, significantly lowering the lithium-ion diffusion barrier and constructing a flexible and rapid ion transport channel; furthermore, the incorporation of transition metals enhances the electronic conductivity and stability of the structure, while easily polarizable hydroxyl groups significantly improve the structural flexibility and interfacial stability of the framework by constructing a dynamic hydrogen bond network. The synergistic effect of these components optimizes the lithium-ion transport kinetics and the electrochemical stability of the material from multiple dimensions, ultimately achieving significant improvements in ionic conductivity, air stability, and electrochemical performance. Summary of the Invention

[0005] To address this significant technological challenge, this invention provides a heteroanion oxyhalide solid electrolyte, its preparation method, applications, and an all-solid-state battery. Through innovative material design concepts, this invention successfully develops a heteroanion oxyhalide solid electrolyte, Li... （3d+2e+2f+g） M m+ b N n+ c (PO4) d (SO4) e (CO3) f (OH) g X (mb+nc) (M is an alkaline earth metal, N is one or more of transition metals, rare earth metals, and p-block metals, and X is at least one of F, Cl, Br, and I). This material employs a unique "metal-halogen co-doping" strategy to construct a flexible anionic framework structure at the molecular level. This innovative design achieves multiple breakthroughs: First, the introduction of halogen atoms to form a twisted Li-X sublattice structure significantly reduces the lithium-ion migration barrier; the addition of alkaline earth metals anchors the anionic framework with divalent metal ions, lowers the activation energy, and improves conductivity; simultaneously, the addition of transition metals and easily polarizable hydroxyl radicals enables room-temperature ionic conductivity to exceed 10. -3 S / cm; Secondly, the special angle-shared oxygen network structure not only expands the lithium-ion transport channel, but also endows the material with excellent mechanical flexibility (Young's modulus <30GPa), ensuring close contact with the electrode material; more importantly, the halogen-rich passivation layer that spontaneously forms on the material surface makes it exhibit excellent environmental stability, and the performance degradation can still be controlled within 20% after 2 hours of air exposure.

[0006] In practical applications, the all-solid-state battery prepared using the solid-state electrolyte of this invention exhibits significant advantages: energy density exceeding 500 Wh / kg, and capacity decay rate of only 5% after 500 cycles. These performance indicators are significantly superior to existing commercial liquid and solid-state battery systems. Furthermore, this material is prepared using a conventional solid-phase method, reducing raw material costs by more than 80% compared to sulfide systems, demonstrating a clear advantage for industrialization. The successful development of this invention not only solves the key material bottleneck in the development of solid-state batteries but also provides solid technical support for promoting the development of the new energy industry towards higher safety and higher energy density, possessing significant scientific and commercial value.

[0007] This invention employs a dual doping strategy of transition metals and halogens to achieve controllable distortion of the crystal structure and optimization of ion transport channels while maintaining structural stability. This addresses the key issues of low ionic conductivity in traditional polyanionic salt electrolytes and poor stability in halide electrolytes. The material's fabrication process is simple and cost-effective, providing an ideal electrolyte solution for the development of high-performance all-solid-state batteries.

[0008] The present invention solves the above-mentioned technical problems through the following technical solutions:

[0009] This invention provides a heteroanion oxyhalide solid electrolyte material with the chemical formula Li. （3d+2e+2f+g） M m + b N n+ c (PO4) d (SO4) e (CO3) f (OH) g X (mb+nc) M is an alkaline earth metal, N is one or more of a transition metal, rare earth metal, and p-block metal, and X is at least one of F, Cl, Br, and I; in the chemical formula, 0.005≤b≤1, 0.1≤c≤2, 0.1≤d≤2, 0.1≤e≤2, 0.1≤f≤2, and 0.1≤g≤2.

[0010] In this invention, the heteroanion oxyhalide solid electrolyte material is preferably in an amorphous state.

[0011] In the invention, m in the chemical formula + n + The valence number of metal M.

[0012] In this invention, the transition metal preferably includes one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, and W, more preferably Ta.

[0013] In this invention, the alkaline earth metal preferably includes one or more of Mg, Ca, Sr and Ba.

[0014] In this invention, the rare earth metal preferably includes one or more of La, Y, Ce, Nd, Dy, Ho, Er and Yb.

[0015] In this invention, the P-region metal preferably includes one or more of Al, Ga, In, Ge, Sn, Pb, Sb, and Bi.

[0016] In this invention, when N includes a transition metal, preferably, 0.01 ≤ b ≤ 1, for example, 0.05, 0.1, 0.13, 0.15, 0.23, 0.33, 0.5, 0.56, 0.75, 0.88, 0.95 or 1.0, and more preferably, 0.05 ≤ b ≤ 0.33.

[0017] In some implementations, when N is Zr, preferably 0.1 ≤ c ≤ 2, for example 0.5, 1.11, 1.2, 1.25, 1.3, 1.43 or 1.67, and more preferably 1 ≤ c ≤ 1.7.

[0018] In some implementations, when N is Ta, preferably 0.5 ≤ c ≤ 2, for example 0.6, 0.8, 1, 1.11, 1.25, 1.43 or 1.67, more preferably 1.2 ≤ c ≤ 1.7 or 0.5 ≤ c ≤ 1.05.

[0019] In some implementations, when N includes a transition metal and "one or more of rare earth metals and P-region metals", preferably 1 ≤ c ≤ 2, for example 1.2, 1.375, 1.5 or 1.8.

[0020] In some preferred embodiments, N includes a transition metal and one or more rare earth metals and P-block metals, and the molar ratio of the transition metal to one or more rare earth metals and P-block metals is 1:(0.05-0.5), and 1≤c≤2.

[0021] In some specific embodiments, the chemical formula of the heteroanion oxyhalide solid electrolyte material is one of the following chemical formulas:

[0022] Li 2.66 Zr 1.67 Ca 0.1(PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 6.88 、

[0023] Li 2.66 Zr 1.43 Ba 0.05 (PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.33 Cl 5.82 、

[0024] Li 2.96 Zr 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH) 0.33 Cl 5.66 、

[0025] Li 3.17 Zr 1.11 Ca 0.1 (PO4) 0.5 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 4.64 、

[0026] Li 2.66 ZrMg 0.33 (PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 4.66 、

[0027] Li 3.17 Hf 1.67 Ba 0.33 (PO4) 0.5 (SO4) 0.16 (CO3) 0.5 (OH) 0.33 Cl 7.34 、

[0028] Li 2.96 Hf 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH)0.33 Cl 5.66 、

[0029] Li 2.66 Hf 1.43 Sr0. 33 (PO4) 0.33 (SO4) 0.44 (CO3) 0.22 (OH) 0.33 Cl 6.38 、

[0030] Li 2.66 Hf 1.25 Ba 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 5.1 、

[0031] Li 2.43 Hf 1.11 Ca 0.1 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.1 Cl 4.64 、

[0032] Li 2.83 HfBa 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.5 Cl 4.1 、

[0033] Li 2.83 Mg 0.1 Zr(PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.5 Cl 4.2 、

[0034] Li 3.17 Ca 0.1 Zr(PO4) 0.5 (SO4) 0.23 (CO3) 0.43 (OH) 0.33 Cl 4.2 、

[0035] Li 2.94 La 0.1 Ba0.05 Zr(PO4) 0.5 (SO4) 0.5 (CO3) 0.16 (OH) 0.1 Cl 4.4 ,

[0036] Li 2.66 Al 0.1 Ba 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 ,

[0037] Li 2.66 Al 0.1 Mg 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 ,

[0038] Li 2.66 ZrSr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Br4Cl 0.1 ,

[0039] Li 2.66 Ta 1.67 Sr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 8.45 .

[0040] In this invention, the ionic conductivity of the heteroanion oxyhalide solid electrolyte material can be 10. -5 S cm -1 -11.5*10 -3 S cm -1 For example, 0.67*10 -3 S cm -1 0.75*10 -3 S cm -1 0.93*10 -3 S cm -1 1.12*10 -3 Scm-1 1.28*10 -3 S cm -1 1.38*10 -3 S cm -1 1.65*10 -3 S cm -1 1.72*10 -3 S cm -1 1.80*10 -3 S cm -1 1.89*10 -3 S cm -1 2.38*10 -3 S cm -1 3.41*10 -3 S cm -1 5.78*10 -3 S cm -1 7.93*10 -3 S cm -1 8.69*10 -3 S cm -1 Or 11.5*10 -3 S cm -1

[0041] This invention also provides a method for preparing the aforementioned heteroanion oxyhalide solid electrolyte material, comprising the following steps: mixing Li3PO4, Li2SO4, Li2CO3, LiOH, and N... n+ X n and M n+ X n The mixture was subjected to high-energy ball milling.

[0042] In this invention, the Li3PO4, Li2SO4, Li2CO3, LiOH, and N... n+ X n and M n+ X n The molar ratio is generally determined based on the values ​​of b, c, d, e, f, and g in the chemical formula of the heteroanion oxyhalide solid electrolyte material.

[0043] The mixing method can be grinding or agitation. The grinding method can be manual or mechanical. The manual mixing time can be 2-20 minutes, for example, 5 minutes or 10 minutes. The mechanical grinding speed can be 0-300 rpm and not 0, preferably 100-250 rpm, for example, 150 rpm.

[0044] In this invention, the preparation process of the heteroanion oxyhalide solid electrolyte material is preferably carried out entirely under the protection of an inert gas. The inert gas is, for example, argon.

[0045] In this invention, according to conventional practice in the art, the high-energy ball milling is generally carried out in a high-energy ball mill, for example, in a planetary high-energy ball mill.

[0046] In this invention, the grinding jar used in the high-energy ball milling process can be made of zirconium dioxide, stainless steel or cemented carbide, and the grinding beads can be made of stainless steel or zirconium dioxide.

[0047] In this invention, the high-energy ball milling speed can be 450-900 rpm, preferably 500-700 rpm, for example 600 rpm. The high-energy ball milling time can be 8-24 hours, preferably 10-20 hours, for example 12 hours.

[0048] In this invention, the diameter of the grinding beads used in the high-energy ball milling process can be 1-40mm, for example 5mm, 10mm, 8mm or 20mm.

[0049] In this invention, during the high-energy ball milling process, the ball-to-material ratio can be (25-70):1, for example, 40:1, 45:1, 50:1 or 55:1, where the ball-to-material ratio refers to the mass ratio of the grinding beads to the raw material.

[0050] The present invention also provides an application of the heteroanion oxyhalide solid electrolyte material as described above in batteries.

[0051] In this invention, the battery is preferably an all-solid-state lithium battery.

[0052] The present invention also provides a battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein one or more of the positive electrode, the negative electrode, and the electrolyte comprise a heteroanion oxyhalide solid electrolyte material as described above. Preferably, the battery is an all-solid-state battery.

[0053] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0054] The reagents and raw materials used in this invention are all commercially available.

[0055] The positive and progressive effects of this invention are as follows:

[0056] The heteroanion oxyhalide solid electrolyte prepared by this invention has extremely high ionic conductivity, excellent air stability and excellent electrochemical stability. Moreover, the preparation method is simple, and it has excellent electrochemical performance when applied to all-solid-state batteries, especially good long-cycle performance. Attached Figure Description

[0057] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings:

[0058] Figure 1 XRD patterns of the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-5 and Li2ZrCl6 prepared in Comparative Example 1;

[0059] Figure 2 The Arrhenius fitting curves are shown for the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-5.

[0060] Figure 3 EIS impedance diagram of Li2ZrCl6 prepared in Comparative Example 1;

[0061] Figure 4 This is a TEM image of the heteroanion oxyhalide solid electrolyte material prepared in Example 4;

[0062] Figure 5 The graph shows the air stability test performance of the heteroanion oxyhalide solid electrolyte material prepared in Example 4.

[0063] Figure 6 The state diagrams of Li2ZrCl6 prepared for Comparative Example 1 and LiTaCl6 prepared for Comparative Example 2 after being placed in a constant temperature and humidity room with a humidity of 20% and a temperature of 25℃ for a period of time.

[0064] Figure 7 The graph shows the long-cycle performance of an all-solid-state battery assembled based on the heteroanion oxyhalide solid electrolyte material prepared in Example 4 in the test example. Detailed Implementation

[0065] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0066] Example 1

[0067] Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4, and CaCl2 were weighed according to a molar ratio of 0.33:0.5:0.16:0.33:1.67:0.1, with a total mass of 1 g. The sample was placed in a mortar and manually mixed for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium dioxide grinding beads. The mixture was ball milled at 600 rpm for 12 h using a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding the heteroanion oxyhalide solid electrolyte material Li. 2.66 Zr 1.67 Ca 0.1 (PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 6.88 All of the above processes were carried out under the protection of argon gas.

[0068] Example 2

[0069] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and BaCl2 were weighed in a molar ratio of 0.33:0.43:0.23:0.33:1.43:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.66 Zr 1.43 Ba 0.05 (PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.33 Cl 5.82 .

[0070] Example 3

[0071] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and SrCl2 were weighed in a molar ratio of 0.43:0.53:0.13:0.33:1.25:0.33, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.96 Zr 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH) 0.33 Cl 5.66 .

[0072] Example 4

[0073] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and CaCl2 were weighed in a molar ratio of 0.5:0.33:0.33:0.33:1.11:0.1, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 3.17 Zr 1.11 Ca 0.1 (PO4) 0.5 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 4.64 .

[0074] Example 5

[0075] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and MgCl2 were weighed in a molar ratio of 0.33:0.5:0.16:0.33:1:0.33, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.66 ZrMg 0.33 (PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 4.66 .

[0076] Example 6

[0077] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and BaCl2 were weighed in a molar ratio of 0.5:0.16:0.5:0.33:1.67:0.33, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 3.17 Hf 1.67 Ba 0.33 (PO4) 0.5 (SO4) 0.16 (CO3) 0.5 (OH) 0.33 Cl 7.34 .

[0078] Example 6

[0079] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and SrCl2 were weighed in a molar ratio of 0.43:0.53:0.13:0.33:1.25:0.33, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.96 Hf 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH) 0.33 Cl 5.66 .

[0080] Example 7

[0081] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.33:0.5:1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.83 HfBa 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.5 Cl 4.1 .

[0082] Example 8

[0083] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.33:0.5:1.25:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.66 Hf 1.25 Ba 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 5.1 .

[0084] Example 9

[0085] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.33:0.1:1.11:0.1, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.43 Hf 1.11 Ca 0.1 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.1 Cl 4.64 .

[0086] Example 10

[0087] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, HfCl4 and SrCl2 were weighed in a molar ratio of 0.33:0.44:0.22:0.5:1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.83 HfBa 0.05 (PO4) 0.33 (SO4) 0.44 (CO3) 0.22 (OH) 0.5 Cl 4.1 .

[0088] Example 11

[0089] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and MgCl2 were weighed in a molar ratio of 0.33:0.43:0.23:0.5:1:0.1, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.83 Mg 0.1 Zr(PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.5 Cl 4.2 .

[0090] Example 12

[0091] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4 and CaCl2 were weighed in a molar ratio of 0.5:0.23:0.43:0.33:1:0.1, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 3.17 Ca 0.1 Zr(PO4) 0.5 (SO4) 0.23 (CO3) 0.43 (OH) 0.33 Cl 4.2 .

[0092] Example 13

[0093] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4, LaCl3, and BaCl2 were weighed in a molar ratio of 0.5:0.5:0.16:0.1:1:0.1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, resulting in the Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4, LaCl3, and BaCl2 solid electrolyte material. 2.94 La 0.1 Ba 0.05 Zr(PO4) 0.5 (SO4) 0.5 (CO3) 0.16 (OH) 0.1 Cl 4.4

[0094] Example 14

[0095] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4, AlCl3, and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.44:0.11:1:0.1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, resulting in the preparation of the heteroanion oxyhalide solid electrolyte material Li. 2.66 Al 0.1 Ba 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 .

[0096] Example 15

[0097] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrCl4, AlCl3, and MgCl2 were weighed in a molar ratio of 0.33:0.33:0.44:0.11:1:0.1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, resulting in the preparation of the heteroanion oxyhalide solid electrolyte material Li. 2.66 Al 0.1 Mg 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 .

[0098] Example 16

[0099] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, ZrBr4 and MgCl2 were weighed in a molar ratio of 0.33:0.33:0.33:0.33:1:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, and the heteroanion oxyhalide solid electrolyte material Li was obtained. 2.66 ZrSr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Br4Cl 0.1 .

[0100] Example 17

[0101] Compared with Example 1, except that Li3PO4, Li2SO4, Li2CO3, LiOH, TaCl5, and SrCl2 were weighed in a molar ratio of 0.33:0.33:0.33:0.33:1.67:0.05, with a total mass of 1g, all other parameters and conditions were the same as in Example 1, resulting in the preparation of the heteroanion oxyhalide solid electrolyte material Li. 2.66 Ta 1.67 Sr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 8.45 All of the above processes were carried out under the protection of argon gas.

[0102] Comparative Example 1

[0103] LiCl and ZrCl4 were weighed at a molar ratio of 2:1, with a total mass of 1 g. The sample was placed in a mortar and manually mixed for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled at 600 rpm for 12 h using a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding Li2ZrCl6. All the above processes were carried out under argon protection.

[0104] Comparative Example 2

[0105] LiCl and TaCl5 were weighed at a 1:1 molar ratio, with a total mass of 1 g. The sample was placed in a mortar and manually mixed for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled at 600 rpm for 12 h using a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding LiTaCl6. All the above processes were carried out under argon protection.

[0106] Comparative Example 3

[0107] Li₂SO₄ and TaCl₅ were weighed at a 1:1 molar ratio, with a total mass of 1 g. The sample was placed in a mortar and manually mixed for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled in a planetary high-energy ball mill at 600 rpm for 12 h. After the reaction was complete, the sample was removed, yielding Li₂TaCl₅SO₄. All the above processes were carried out under argon protection.

[0108] Comparative Example 4

[0109] Li₃PO₄ and TaCl₅ were weighed at a molar ratio of 0.67:1, with a total mass of 1 g. The sample was manually mixed in a mortar for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled at 600 rpm for 12 h in a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding Li₂TaCl₅P. 0.67 O 2.68 All of the above processes were carried out under the protection of argon gas.

[0110] Comparative Example 5

[0111] Li3PO4, Li2SO4, Li2CO3, HfCl4, and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.33:1.25:0.05, with a total mass of 1 g. The sample was manually mixed in a mortar for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled at 600 rpm for 12 h in a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding Li. 2.33 Ba 0.05 Hf 1.25( PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 5.1 All of the above processes were carried out under the protection of argon gas.

[0112] Comparative Example 6

[0113] Li3PO4, Li2SO4, Li2CO3, ZrCl4, and SrCl2 were weighed in a molar ratio of 0.33:0.33:0.33:1.25:0.05, with a total mass of 1 g. The sample was placed in a mortar and manually mixed for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled in a planetary high-energy ball mill at 600 rpm for 12 h. After the reaction was complete, the sample was removed, yielding Li. 2.33 Sr 0.05 Zr 1.25( PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 5.1 All of the above processes were carried out under the protection of argon gas.

[0114] Comparative Example 7

[0115] Li3PO4, Li2SO4, Li2CO3, TaCl5, and BaCl2 were weighed in a molar ratio of 0.33:0.33:0.33:1.67:0.05, with a total mass of 1 g. The sample was manually mixed in a mortar for 10 min, then placed in a 50 mL ball mill jar containing 50 g of 5 mm diameter zirconium grinding beads. The mixture was ball milled at 600 rpm for 12 h in a planetary high-energy ball mill. After the reaction was complete, the sample was removed, yielding Li... 2.33 Ta 1.67 Ba 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 8.45 All of the above processes were carried out under the protection of argon gas.

[0116] Test case

[0117] (1) Morphological characterization and XRD testing

[0118] according to Figure 1 and Figure 4 It can be seen that the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-10 are mainly amorphous, with small microcrystal particles interspersed. Moreover, long-range ordered lattice arrangement is observed in the amorphous sequence through TEM high-resolution mode.

[0119] (2) Ionic conductivity test

[0120] At different temperatures (25-80℃), 100-120 mg of the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-17, Li2ZrCl6 prepared in Comparative Example 1, LiTaCl6 prepared in Comparative Example 2, Li2TaCl5SO4 prepared in Comparative Example 3, and Li2TaCl5P prepared in Comparative Example 4 were taken respectively. 0.67 O 2.68 And Li, in comparison example 5 2.33 Ba 0.05 Hf 1.25( PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 5.1 Comparative Example 6 Li 2.33 Sr 0.05 Zr 1.25( PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 5.1 Comparative Example 7 Li 2.33 Ta 1.67 Ba 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 Cl 8.45 The sample was placed in a mold and pressed at 300 MPa to form a thin sheet with a diameter of 10 mm and a thickness of 0.62 mm. The two ends of the mold were connected to an Autolab for electrochemical impedance spectroscopy (EIS) testing. The test results are shown in Table 1 and [Table data missing]. Figures 3-4 Wherein, ionic conductivity ρ = L / RS, L is 0.62 mm, S represents the area of ​​a circle with a diameter of 10 mm, and R is the impedance.

[0121] 10 -5 S cm -1 -11.5*10 -3 S cm -1For example, 0.67*10 -3 S cm -1 0.75*10 -3 S cm -1 0.93*10 - 3 S cm -1 1.12*10 -3 S cm -1 1.28*10 -3 S cm -1 1.38*10 -3 S cm -1 1.65*10 -3 S cm -1 1.72*10 -3 Scm -1 1.80*10 -3 S cm -1 1.89*10 -3 S cm -1 2.38*10 -3 S cm -1 3.41*10 -3 S cm -1 5.78*10 -3 S cm -1 7.93*10 -3 S cm -1 8.69*10 -3 S cm -1 Or 11.5*10 -3 S cm -1 .

[0122] Figure 2 The Arrhenius fitting curves are shown for the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-5; Figure 2 It can be seen that the conductivity of Examples 1-5 is linearly related to the reciprocal of temperature (1000 / T, where T is the absolute temperature in Kelvin K).

[0123] Table 1. Ionic conductivity at room temperature of the heteroanion oxide halide solid electrolyte materials prepared in Examples 1-17 and Comparative Examples 1-7

[0124]

[0125] Table 2. Ionic conductivity of the heteroanion oxyhalide solid electrolyte materials prepared in Examples 1-5 at different temperatures.

[0126]

[0127] According to the test data, the heteroanion oxyhalide solid electrolyte material has excellent ionic conductivity, which is sufficient to meet the application of all-solid-state batteries. However, the materials prepared by Comparative Examples 1-6 have low ionic conductivity and poor electrochemical performance.

[0128] (3) Air stability test

[0129] Figure 5 This is a graph showing the air stability test performance of the heteroanion oxyhalide solid electrolyte material prepared in Example 10. The blue curve represents the direct test result of the heteroanion oxyhalide solid electrolyte material prepared in Example 10, while the red curve represents the test result after placing the heteroanion oxyhalide solid electrolyte material prepared in Example 10 in a constant temperature and humidity room at 25°C and 20% humidity for 2 hours, followed by vacuum drying. According to the test results, the conductivity before air exposure is 1.72 mS / cm. -1 The value after exposure was 1.23 mS cm⁻¹. -1 This demonstrates that the heteroanion oxyhalide solid electrolyte material prepared in Example 10 has excellent air stability.

[0130] according to Figure 6 It can be seen that the Li2ZrCl6 material prepared in Comparative Example 1 liquefies after being placed in air for 2 hours, while the LiTaCl6 prepared in Comparative Example 2 completely liquefies after being placed in air for 2 hours, making it impossible to test its conductivity.

[0131] (4) Electrochemical performance testing

[0132] Testing equipment: Wuhan Land Battery Testing System (Land CT2001A)

[0133] Composite cathode preparation: The heteroanion oxyhalide solid electrolyte material prepared in Example 4 was manually mixed with lithium cobalt oxide in a mortar at a mass ratio of 3:7 until homogeneous.

[0134] Solid-state battery assembly: A fully solid-state battery was assembled using LiIn alloy as the negative electrode, Li6PS5Cl as the transition layer, the heteroanion oxyhalide solid electrolyte material prepared in Example 4 as the electrolyte layer, and the aforementioned composite positive electrode as the positive electrode. The specific steps were as follows: 40 mg of Li6PS5Cl was weighed and placed in the solid-state battery mold, and pressed at 0.5t for 1 min; then 40 mg of the heteroanion oxyhalide solid electrolyte material prepared in Example 4 was weighed and placed on top of the Li6PS5Cl, and pressed at 1.5t for 1 min; then 10 mg of the composite positive electrode was weighed and placed on top of the prepared heteroanion oxyhalide solid electrolyte material, and pressed at 4t for 5 min; finally, the In and Li sheets were attached to the other side of the Li6PS5Cl, and the mold was held at 2t pressure. The assembly process was carried out in a vacuum glove box filled with high-purity argon gas.

[0135] Electrochemical performance testing was conducted after assembly.

[0136] The test conditions for discharge capacity, first-efficiency rating, and rate performance were as follows: at room temperature, constant current charge-discharge from 0.1-4C followed by 1C long-cycle charging, with a voltage range of 2.8–4.2V. The test results are shown below. Figure 7 And Table 3.

[0137] Table 3. Electrochemical performance test results of all-solid-state batteries assembled based on the heteroanion oxyhalide solid electrolyte material prepared in Example 4.

[0138]

[0139] according to Figure 7 As shown in Table 3, the heteroanion oxyhalide solid electrolyte material prepared by this invention has good long cycle performance of all-solid-state batteries; the capacity retention rate reaches 71% after 1200 cycles.

[0140] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A heteroanion oxyhalide solid electrolyte material, characterized in that, The electrolyte material has the chemical formula Li. （3d+2e+2f+g） M m+ b N n+ c (PO4) d (SO4) e (CO3) f (OH) g X (mb+nc) M is an alkaline earth metal; N is one or more of transition metals, rare earth metals, and p-block metals, including transition metals; X is at least one of F, Cl, Br, and I; in the chemical formula, 0.005≤b≤1, 1≤c≤2, 0.1≤d≤2, 0.1≤e≤2, 0.1≤f≤2, 0.1≤g≤2; in the chemical formula, m + n + The valence number of metals M and N.

2. The heteroanion oxyhalide solid electrolyte material according to claim 1, characterized in that, The alkaline earth metals include one or more of Mg, Ca, Sr and Ba; The transition metals include one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, and W; The rare earth metals include one or more of La, Y, Ce, Nd, Dy, Ho, Er, and Yb; The P-region metal includes one or more of Al, Ga, In, Ge, Sn, Pb, Sb, and Bi.

3. The heteroanion oxyhalide solid electrolyte material according to claim 1, characterized in that, When N contains a transition metal, 0.01 ≤ b ≤ 1; And / or, N is Zr; And / or, N is Ta.

4. The heteroanion oxyhalide solid electrolyte material according to claim 1, characterized in that, When N includes a transition metal and "one or more of rare earth metals and P-block metals", the molar ratio of the transition metal and "one or more of rare earth metals and P-block metals" is 1:(0.05-0.5).

5. The heteroanion oxyhalide solid electrolyte material according to claim 1, characterized in that, The heteroanion oxyhalide solid electrolyte material has one of the following chemical formulas: Li 2.66 Zr 1.67 Ca 0.1 (PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 6.88 、 Li 2.66 Zr 1.43 Ba 0.05 (PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.33 Cl 5.82 、 Li 2.96 Zr 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH) 0.33 Cl 5.66 、 Li 3.17 Zr 1.11 Ca 0.1 (PO4) 0.5 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 4.64 、 Li 2.66 ZrMg 0.33 (PO4) 0.33 (SO4) 0.5 (CO3) 0.16 (OH) 0.33 Cl 4.66 、 Li 3.17 Hf 1.67 Ba 0.33 (PO4) 0.5 (SO4) 0.16 (CO3) 0.5 (OH) 0.33 Cl 7.34 、 Li 2.96 Hf 1.25 Sr0. 33 (PO4) 0.43 (SO4) 0.53 (CO3) 0.13 (OH) 0.33 Cl 5.66 、 Li 2.66 Hf 1.43 Sr0. 33 (PO4) 0.33 (SO4) 0.44 (CO3) 0.22 (OH) 0.33 Cl 6.38 、 Li 2.66 Hf 1.25 Ba 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 5.1 、 Li 2.43 Hf 1.11 Ca 0.1 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.1 Cl 4.64 、 Li 2.83 HfBa 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.5 Cl 4.1 、 Li 2.83 Mg 0.1 Zr(PO4) 0.33 (SO4) 0.43 (CO3) 0.23 (OH) 0.5 Cl 4.2 、 Li 3.17 Ca 0.1 Zr(PO4) 0.5 (SO4) 0.23 (CO3) 0.43 (OH) 0.33 Cl 4.2 、 Li 2.94 La 0.1 Ba 0.05 Zr(PO4) 0.5 (SO4) 0.5 (CO3) 0.16 (OH) 0.1 Cl 4.4 、 Li 2.66 Al 0.1 Ba 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 、 Li 2.66 Al 0.1 Mg 0.05 Zr(PO4) 0.33 (SO4) 0.33 (CO3) 0.44 (OH) 0.11 Cl 4.4 、 Li 2.66 ZrSr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Br4Cl 0.1 、 Li 2.66 Ta 1.67 Sr 0.05 (PO4) 0.33 (SO4) 0.33 (CO3) 0.33 (OH) 0.33 Cl 8.45 。 6. A method for preparing a heteroanion oxyhalide solid electrolyte material according to any one of claims 1-5, characterized in that, The method includes the following steps: According to the stoichiometric relationship of chemical formulas, Li3PO4, Li2SO4, Li2CO3, LiOH, and M... m+ X m and N n+ X n After mixing, the mixture is subjected to high-energy ball milling.

7. The method for preparing the heteroanion oxyhalide solid electrolyte material according to claim 6, characterized in that, The mixing method is grinding or vibration mixing; the grinding is manual or mechanical grinding, the manual grinding time is 2-20 minutes, and the mechanical grinding speed is 0-300 rpm and not 0. And / or, the preparation of the heteroanion oxyhalide solid electrolyte material is carried out under inert gas protection throughout the entire process; And / or, the grinding jar used in the high-energy ball milling process is made of zirconium dioxide, stainless steel or cemented carbide, and the grinding beads are made of stainless steel or zirconium dioxide. And / or, the high-energy ball mill rotates at a speed of 450-900 rpm and the high-energy ball milling time is 8-24 h; And / or, in the high-energy ball milling process, the diameter of the grinding beads used is 1-40mm; the ball-to-material ratio is (25-70):

1.

8. Use of a heteroanion oxyhalide solid electrolyte material according to any one of claims 1-5 in a battery.

9. The use according to claim 8, characterized in that, The battery is an all-solid-state lithium battery; at least one of the positive electrode, negative electrode and electrolyte of the all-solid-state lithium battery contains the heteroanion oxyhalide solid electrolyte material.

10. An all-solid-state lithium battery, comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that, At least one of the positive electrode, negative electrode, and electrolyte contains a heteroanion oxyhalide solid electrolyte material as described in any one of claims 1-5.

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