Preparation method of lithium supplement agent, lithium supplement agent and all-solid-state battery

Abstract

The invention discloses a preparation method of a lithium supplement agent, the lithium supplement agent and an all-solid-state battery. The method comprises the following steps: providing raw materials; wherein the raw materials comprise a stable-valence metal oxide raw material and a lithium raw material; mixing the raw materials to obtain a first intermediate product; and carrying out heat treatment on the first intermediate product in a flowing compressed air atmosphere to obtain the lithium supplement agent. By adopting the metal oxide with stable valence state as the raw material, the redox side reaction is not easy to occur in the air environment, the use of inert gas as protective gas is avoided, the preparation cost is reduced, and the obtained lithium supplementing agent has excellent lithium supplementing performance.

Description

Technical Field

[0001] The present invention relates to the field of all-solid-state batteries, and in particular to a preparation method of a lithium supplement, a lithium supplement and an all-solid-state battery. Background Art

[0002] The role of the lithium replenisher is to offset the active lithium consumed by the production of the solid electrolyte interface film and side reactions during the first cycle of charging of the all-solid-state battery. Compared with the negative electrode lithium replenishment technology, the positive electrode lithium replenishment method is simpler and safer. The current method of preparing lithium replenishers uses inert gases, which leads to high costs, difficulties in mass production, and the need for waste gas treatment. Summary of the invention

[0003] In view of the above problems, the object of the present invention is to provide a method for preparing a lithium supplement without using an inert gas, a lithium supplement and an all-solid-state battery. The technical solution is as follows:

[0004] In one aspect, a method for preparing a lithium supplement is provided, the method comprising:

[0005] Providing raw materials; the raw materials include metal oxide raw materials with stable valence and lithium raw materials;

[0006] mixing the raw materials to obtain a first intermediate product;

[0007] The first intermediate product is heat-treated under a flowing compressed air atmosphere to obtain the lithium supplement agent.

[0008] In an exemplary embodiment, the heat treatment includes a first heat treatment stage, a second heat treatment stage, and a temperature reduction stage;

[0009] The heating rate of the first heat treatment stage is 1-5°C / min, the temperature of the first heat treatment stage is 300-700°C, the time of the first heat treatment stage is 2-10h, and the air flow rate of the compressed air in the first heat treatment stage is 10-20L / min;

[0010] The heating rate of the second heat treatment stage is 3-5°C / min, the temperature of the second heat treatment stage is 500-900°C, the time of the second heat treatment stage is 8-20h, and the air flow rate of the compressed air in the second heat treatment stage is 3-10L / min;

[0011] The air flow rate of the compressed air in the cooling stage is 1 to 5 L / min.

[0012] In an exemplary embodiment, the valence-stable metal oxide raw material includes one or more combinations of Fe2O3, CuO, NiO, MnO2 or CoO.

[0013] In an exemplary embodiment, the lithium raw material includes one or more combinations of Li2O, LiOH, Li2CO3, LiNO3 or Li2SO4.

[0014] In an exemplary embodiment, the mass ratio of the metal oxide raw material with stable valence to the lithium raw material is 1:(0.1-10).

[0015] In an exemplary embodiment, mixing the raw materials to obtain a first intermediate product comprises:

[0016] Using a grinding mill, mixing the raw materials to obtain the first intermediate product;

[0017] The mixing time is 1 to 10 minutes, and the mixing speed is 200 to 1000 rpm.

[0018] In an exemplary embodiment, the step of heat-treating the first intermediate product under a flowing compressed air atmosphere to obtain the lithium supplement comprises:

[0019] Under the flowing compressed air atmosphere, heat-treating the first intermediate product to obtain a second intermediate product;

[0020] Refining the second intermediate product to obtain a third intermediate product;

[0021] The third intermediate product is screened to obtain the lithium supplement agent.

[0022] In an exemplary embodiment, the screening the third product to obtain the lithium supplement comprises:

[0023] The third intermediate product is sieved using a sieve to obtain the lithium supplement; the mesh size of the sieve ranges from 200 to 400 meshes.

[0024] On the other hand, the present invention further provides a lithium supplement, including the lithium supplement prepared by any of the preparation methods described above.

[0025] On the other hand, the present invention also provides an all-solid-state battery, comprising the lithium supplement agent described above.

[0026] The present invention discloses a method for preparing a lithium supplement, which comprises: providing raw materials; wherein the raw materials comprise a metal oxide raw material with a stable valence state and a lithium raw material; mixing the raw materials to obtain a first intermediate product; and heat treating the first intermediate product in a flowing compressed air atmosphere to obtain a lithium supplement. By using a metal oxide with a stable valence state as a raw material, the lithium supplement has high stability at high temperatures, avoids oxidation-reduction side reactions in an air environment, thereby avoiding the use of an inert gas as a protective gas, reducing the preparation cost, and the obtained lithium supplement has excellent lithium supplement performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solution of the present invention, the following briefly introduces the drawings required for use in the embodiments or prior art descriptions. Obviously, the drawings described below are only some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 This is a flow chart of a method for preparing a lithium supplement provided by an embodiment of the present invention;

[0029] Figure 2 is an XRD diagram of Li5FeO4 provided in an embodiment of the present invention;

[0030] Figure 3 is a SEM image of Li5FeO4 provided in an embodiment of the present invention;

[0031] Figure 4 is an XRD diagram of Li6CoO4 provided in an embodiment of the present invention;

[0032] Figure 5 It is a SEM image of Li6CoO4 provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] At present, the research on lithium supplements is mainly to mix metal oxides and lithium salts and introduce inert gas for high-temperature sintering. The preparation process needs to be completed in an inert gas environment, mainly because lithium supplements are sensitive to the air environment, but the introduction of inert gas is undoubtedly not conducive to reducing the cost of material synthesis, and there is relatively little research on lithium supplements in solid-state battery systems. The introduction of a certain flow of inert gas (nitrogen or argon) for sintering at a higher temperature is not only costly, but also difficult to mass produce and has problems such as waste gas treatment.

[0035] Therefore, it is very necessary to develop a low-cost, mass-producible preparation method that does not require waste gas treatment to prepare lithium supplements.

[0036] The present application provides a method for preparing a lithium supplement. Figure 1 , Figure 1 The present invention is a flow chart of a method for preparing a lithium supplement, the method comprising the following steps:

[0037] Step S1: providing raw materials; the raw materials include metal oxide raw materials with stable valence and lithium raw materials.

[0038] Specifically, the present application believes that since unstable valence metal oxides are selected as raw materials, redox side reactions are prone to occur under air environment conditions, thereby causing the lithium supplement agent to fail and affecting the lithium supplement effect of the lithium supplement agent. Therefore, stable valence metal oxides are selected as raw materials. The stable valence metal oxides are not prone to redox side reactions under air environment conditions. Therefore, when the stable valence metal oxides are used as raw materials to react with lithium raw materials, there is no need to use inert gas protection, thereby reducing costs, avoiding the problem of waste gas treatment, and avoiding the problem of lithium supplement agent failure.

[0039] Step S2: Mix the raw materials to obtain a first intermediate product.

[0040] Specifically, there are many ways to mix the raw materials, such as high-energy ball milling with a ball mill, grinding with a pulverizer, etc. The appropriate mixing method can be selected according to actual needs.

[0041] Step S3: heat-treating the first intermediate product in a flowing compressed air atmosphere to obtain a lithium supplement.

[0042] Specifically, by using flowing compressed air as the sintering atmosphere, the gases such as H2O, CO2, NO / NO2, SO2, etc. produced by the high-temperature decomposition of lithium salts are taken away, the purity of lithium supplement reagents is improved, the cost can be effectively reduced, and it is extremely easy to mass produce. The heat treatment process is the process of crystal phase formation. The crystal phase structure directly affects the conductivity of the material. The crystal structure of the material is regulated by heat treatment to obtain the target crystal phase, thereby obtaining a lithium supplement material with excellent conductive properties.

[0043] In the embodiment of the present application, the heat treatment includes a first heat treatment stage, a second heat treatment stage and a cooling stage;

[0044] The heating rate of the first heat treatment stage is 1-5°C / min, the temperature of the first heat treatment stage is 300-700°C, the time of the first heat treatment stage is 2-10h, and the air flow rate of the compressed air in the first heat treatment stage is 10-20L / min;

[0045] The heating rate of the second heat treatment stage is 3-5°C / min, the temperature of the second heat treatment stage is 500-900°C, the time of the second heat treatment stage is 8-20h, and the air flow rate of the compressed air in the second heat treatment stage is 3-10L / min;

[0046] The air flow rate of the compressed air in the cooling stage is 1 to 5 L / min.

[0047] Specifically, the embodiments of the present application take into account that maintaining a high gas flow rate during the first heat treatment stage is to allow the H2O, CO2, NO / NO2, SO2 and other gases generated by the high-temperature decomposition of the lithium salt to be quickly released to avoid the residual effects on the material due to insufficient release. This stage step is relatively important and requires maintaining a sufficient gas flow rate; and the embodiments of the present application take into account that during sintering during the second heat treatment stage, since the reaction at this time is mainly in the form of a two-phase solid solution, a lower gas flow rate can promote the formation of the lithium supplement agent; the embodiments of the present application take into account that when cooling, since the crystalline phase of the lithium supplement material has been formed, only a small amount of gas needs to be introduced; it is worth noting that the discharge should be completed when the temperature is around 200°C to avoid the temperature being too low, which may cause serious side reactions between the moisture in the air and the residual lithium on the surface of the material.

[0048] On the other hand, the embodiment of the present application can also control the formation of the crystalline phase by adjusting the heating rate parameters, temperature, and time of the heat treatment stage, so as to obtain a lithium supplement with high conductivity. It should be noted that the flowing compressed air is introduced at the first heat treatment stage when the temperature starts to rise, that is, according to the set airflow rate of the compressed air in the first heat treatment stage, and then the second heat treatment stage starts to rise, that is, according to the set airflow rate of the compressed air in the second heat treatment stage; the time of the heat treatment in each stage is calculated from the time when the temperature is raised to the set temperature. For example, after the first heat treatment stage is heated to the set temperature, the timing and heat preservation are started until the set time of the first heat treatment stage is met. Similarly, after the second heat treatment stage is heated to the set temperature, the timing and heat preservation are started until the set time of the second heat treatment stage is met.

[0049] In the embodiment of the present application, the metal oxide raw material with a stable valence state includes one or more combinations of Fe2O3, CuO, NiO, MnO2 or CoO.

[0050] Specifically, iron metal oxides include ferric dioxide (FeO), iron oxide (Fe2O3) and ferroferric oxide (Fe3O4); the iron element in ferric dioxide is in a divalent state, and the iron element in ferroferric oxide (Fe3O4) is in a divalent state and a trivalent state; the trivalent iron element is more stable than the divalent iron element and is not prone to redox reactions, so iron oxide (Fe2O3) has higher stability as a raw material for the embodiments of the present application.

[0051] Copper oxides include cuprous oxide (Cu2O) and cupric oxide (CuO). Compared with the monovalent copper element in cuprous oxide, the divalent copper element in cupric oxide is more stable, so cupric oxide is selected as the raw material of the embodiment of the present application.

[0052] Under the reaction conditions disclosed in the examples of the present application, among nickel oxides, nickel oxide is less likely to undergo redox side reactions in an air environment without the protection of an inert gas, so nickel oxide is selected as the raw material of the examples of the present application.

[0053] Manganese oxides include manganese oxide (MnO), manganese dioxide (MnO), dimanganese trioxide (Mn O), and trimanganese tetraoxide (Mn O). The manganese element in manganese dioxide is tetravalent and has high stability. Therefore, manganese dioxide is selected as the raw material of the embodiment of the present application.

[0054] Cobalt oxides include cobalt oxide (CoO), cobalt trioxide (Co2O3) and cobalt tetraoxide (Co3O4); among them, cobalt oxide (CoO) is more stable in high temperature and air environment, so cobalt oxide with higher stability is selected as the raw material.

[0055] By selecting metal oxides with stable valence as the raw materials of the embodiments of the present application, redox side reactions can be directly avoided in an air environment, and no inert gas protection is required, thereby reducing the preparation cost.

[0056] In the embodiments of the present application, the lithium raw material includes one or more combinations of Li2O, LiOH, Li2CO3, LiNO3 or Li2SO4.

[0057] Specifically, the selection of lithium raw materials can be set according to actual needs. One or two or more combinations of lithium salts can be selected as raw materials. For example, LiOH is selected as the raw material of the embodiment of the present application to introduce the lithium element.

[0058] In the embodiments of the present application, the mass ratio of the metal oxide in a stable valence state to the lithium raw material is 1:(0.1-10).

[0059] Specifically, by changing the mass ratio of the stable valence metal oxide raw material and the lithium raw material, the ratio between the high-valence metal element and the lithium element in the lithium supplement can be regulated, thereby improving the conductivity of the lithium supplement, and further improving the energy density and cycle performance of the battery.

[0060] In the embodiment of the present application, the raw materials are mixed to obtain the first intermediate product, which includes:

[0061] Using a mill, the raw materials are mixed to obtain a first intermediate product;

[0062] The mixing time is 1 to 10 minutes, and the mixing speed is 200 to 1000 rpm.

[0063] Specifically, the raw materials are mixed by using a grinding machine, the mixing speed is adjusted to improve the mixing efficiency, and the mixing time is controlled to make the raw materials mixed evenly.

[0064] In the embodiment of the present application, the first intermediate product is heat treated under a flowing compressed air atmosphere to obtain a lithium supplement comprising:

[0065] heat-treating the first intermediate product in a flowing compressed air atmosphere to obtain a second intermediate product;

[0066] Refining the second intermediate product to obtain a third intermediate product;

[0067] The third intermediate product is screened to obtain a lithium supplement.

[0068] Specifically, after the first intermediate product is heat-treated, the second intermediate product directly obtained has larger particles. The second intermediate product can be refined to obtain a third intermediate product with smaller particles, and then the product with larger particles is removed through screening to obtain a lithium supplement with small particles and uniform particle size, so that the lithium supplement maintains a high interface contact with the electrode material, and replenishes lithium more effectively during the battery charging and discharging process, thereby playing a role in offsetting the active lithium consumed by the generation of the interface SEI film and the side reactions during the first cycle of charging, thereby improving the energy density and stability of the battery and extending the service life of the battery. On the other hand, the lithium supplement obtained by the refinement process improves the interface contact and can also reduce the probability of safety problems such as internal short circuits in the battery, thereby improving the safety performance of the battery.

[0069] In the embodiment of the present application, the third product is screened to obtain a lithium supplement comprising:

[0070] The third intermediate product is sieved using a sieve to obtain a lithium supplement; the mesh number of the sieve ranges from 200 to 400 meshes.

[0071] Specifically, a sieve can be selected for screening, wherein the specific mesh size of the sieve can be set according to specific needs, so as to obtain a lithium supplement with a suitable particle size, improve interface contact, thereby improving the energy density and stability of the battery, and extending the service life and safety performance of the battery.

[0072] The embodiments of the present application also provide a lithium supplement, including a lithium supplement prepared by any preparation method disclosed in the embodiments of the present application.

[0073] Specifically, the embodiment of the present application provides raw materials; the raw materials include metal oxide raw materials with stable valence and lithium raw materials; wherein the metal oxide with stable valence includes one or more combinations of Fe2O3, CuO, NiO, MnO2 or CoO, and the lithium raw materials include one or more combinations of Li2O, LiOH, Li2CO3, LiNO3 or Li2SO4. The raw materials are mixed, specifically, a mill can be used for mixing to obtain a first intermediate product; the first intermediate product is heat-treated in a flowing compressed air atmosphere, and the heat treatment is a process of performing a first heat treatment stage, a second heat treatment stage and a cooling stage in a flowing compressed air atmosphere. After the heat treatment, the product can also be further refined and screened to finally obtain a lithium supplement.

[0074] The embodiments of the present application also provide an all-solid-state battery, comprising any lithium supplement disclosed in the embodiments of the present application.

[0075] Specifically, the all-solid-state battery comprises a positive electrode, a negative electrode, and an electrolyte. The positive electrode material at least comprises NCM ternary and any lithium supplement disclosed in the present application, and the NCM material includes but is not limited to NCM811, NCM622, NCM523, etc., wherein the content of the lithium supplement in the positive electrode material is 0.1% to 10%; the mixing method is preferably selected from ball milling, grinding, powder mixing, etc. The electrolyte is preferably selected from Li7P3S 11 , Li6PS5Cl, Li3PS4, Li7P2S8, Li 10 GeP2S 12 The negative electrode is preferably selected from one of lithium metal, lithium indium alloy, graphite, silicon or silicon alloy, and silicon dioxide.

[0076] The present invention has no special requirements for the preparation of the battery, and the conventional preparation method of the all-solid-state lithium battery in the art can be adopted. The specific preparation process is well known in the field of solid-state batteries and will not be described in detail here.

[0077] The technical solution of the present application is described below in conjunction with specific embodiments.

[0078] Example 1

[0079] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0080] Fe2O3 and Li2O are weighed at a mass ratio of 1:1.03, and 10g of Fe2O3 and 10.3g of Li2O are added to the mill for 5 minutes and a mixing speed of 500rpm. After the mixture is evenly mixed, the powder is poured into a crucible and transferred to a muffle furnace for heat treatment. The heat treatment process is as follows: the heating rate of the first stage of heat treatment is 2℃ / min, the temperature of the first stage of heat treatment is 400℃, the time of the first stage of heat treatment is 5h, and the air flow rate of compressed air in the first stage of heat treatment is 15L / min; subsequently, the heating rate of the second stage of heat treatment is 5℃ / min, the temperature of the second stage of heat treatment is 800℃, the time of the second stage of heat treatment is 10h, and the air flow rate of compressed air in the second stage of heat treatment is 5L / min; the air flow rate of compressed air in the cooling stage is 1L / min. When the temperature drops to 200℃, quickly transfer it to the glove box, grind it into fine powder, and pass it through a 300-mesh sieve to finally obtain Li5FeO4 lithium supplement reagent. For its XRD pattern, please refer to Figure 2 The standard sheet used in XRD testing is PDF No.75-1253, and its SEM image can be found in 3.

[0081] Follow the steps below to apply the Li5FeO4 in this example to the ternary material to assemble an all-solid-state battery.

[0082] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary, solid electrolyte, Li5FeO4 lithium supplement reagent, and conductive agent in a mass ratio of 78:15:6:1. The positive electrode active material loading is 20 mg / cm 2 The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 Solid-state batteries were assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge tests. The voltage window for battery charge and discharge is 2 to 4.3V. The cycle test was performed at 0.33C charge / 0.33C discharge for 50 cycles.

[0083] Example 2

[0084] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0085] Compared with Example 1, the lithium raw material is LiOH, and other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0086] Example 3

[0087] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0088] Compared with Example 1, the lithium raw material is Li2CO3, and other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0089] Example 4

[0090] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0091] Compared with Example 1, the lithium raw material is LiNO3, and other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0092] Example 5

[0093] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0094] Compared with Example 1, the lithium raw material is Li2SO4, and other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0095] Example 6

[0096] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0097] Compared with Example 1, Fe2O3:Li2O is in a mass ratio of 1:0.1, and 10g of Fe2O3 and 1g of Li2O are weighed respectively; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0098] Example 7

[0099] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0100] Compared with Example 1, Fe2O3:Li2O is in a mass ratio of 1:10, and 10g of Fe2O3 and 100g of Li2O are weighed respectively; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0101] Example 8

[0102] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0103] Compared with Example 1, the mixing time is 1 min; other conditions remain unchanged, and finally the Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0104] Example 9

[0105] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0106] Compared with Example 1, the mixing time is 10 minutes; other conditions remain unchanged, and finally the Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0107] Example 10

[0108] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0109] Compared with Example 1, the mixing speed is 200 rpm; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0110] Embodiment 11

[0111] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0112] Compared with Example 1, the mixing speed is 1000 rpm; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0113] Example 12

[0114] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0115] Compared with Example 1, the heating rate of the first stage of heat treatment is 1°C / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0116] Embodiment 13

[0117] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0118] Compared with Example 1, the heating rate of the first stage of heat treatment is 5°C / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0119] Embodiment 14

[0120] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0121] Compared with Example 1, the temperature of the first stage of heat treatment is 300°C; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0122] Embodiment 15

[0123] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0124] Compared with Example 1, the temperature of the first stage of heat treatment is 700°C; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0125] Example 16

[0126] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0127] Compared with Example 1, the time of the first stage of heat treatment is 2 hours; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0128] Embodiment 17

[0129] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0130] Compared with Example 1, the time of the first stage of heat treatment is 10 hours; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0131] Embodiment 18

[0132] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0133] Compared with Example 1, the air flow rate of compressed air in the first heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0134] Embodiment 19

[0135] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0136] Compared with Example 1, the air flow rate of compressed air in the first heat treatment stage is 20 L / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0137] Embodiment 20

[0138] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0139] Compared with Example 1, the heating rate of the second heat treatment stage is 3°C / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0140] Embodiment 21

[0141] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0142] Compared with Example 1, the temperature of the second heat treatment stage is 500°C; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0143] Embodiment 22

[0144] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0145] Compared with Example 1, the temperature of the second heat treatment stage is 900°C; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0146] Embodiment 23

[0147] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0148] Compared with Example 1, the time of the second heat treatment stage is 8 hours; other conditions remain unchanged, and finally the Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0149] Embodiment 24

[0150] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0151] Compared with Example 1, the time of the second heat treatment stage is 20 hours; other conditions remain unchanged, and finally the Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0152] Embodiment 25

[0153] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0154] Compared with Example 1, the air flow rate of compressed air in the second heat treatment stage is 3L / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0155] Embodiment 26

[0156] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0157] Compared with Example 1, the air flow rate of compressed air in the second heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0158] Embodiment 27

[0159] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0160] Compared with Example 1, the air flow rate of compressed air in the cooling stage is 5 L / min; other conditions remain unchanged, and finally Li5FeO4 lithium supplement reagent is obtained. According to the steps in Example 1, the Li5FeO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0161] Embodiment 28

[0162] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0163] Compared with Example 1, a 200-mesh sieve was used; other conditions remained unchanged, and finally a Li5FeO4 lithium supplement reagent was obtained. According to the steps in Example 1, the Li5FeO4 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0164] Embodiment 29

[0165] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0166] Compared with Example 1, a 400-mesh sieve was used; other conditions remained unchanged, and finally a Li5FeO4 lithium supplement reagent was obtained. According to the steps in Example 1, the Li5FeO4 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0167] Embodiment 30

[0168] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0169] CoO and LiOH are weighed at a mass ratio of 1:1.92, and 10g of CoO and 19.2g of LiOH are added to the mill. The mixing time is 2min and the mixing speed is 1000rpm. After the mixture is evenly mixed, the powder is poured into a crucible and transferred to a muffle furnace for heat treatment. The heat treatment process is as follows: the heating rate of the first heat treatment stage is 3℃ / min, the temperature of the first heat treatment stage is 450℃, the time of the first heat treatment stage is 4h, and the air flow rate of the compressed air in the first heat treatment stage is 20L / min; subsequently, the heating rate of the second heat treatment stage is 5℃ / min, the temperature of the second heat treatment stage is 750℃, the time of the second heat treatment stage is 15h, and the air flow rate of the compressed air in the second heat treatment stage is 5L / min; the air flow rate of the compressed air in the cooling stage is 1L / min. When the temperature drops to 200℃, quickly transfer it to the glove box, grind it finely, and pass it through a 300-mesh sieve. Finally, Li6CoO4 lithium supplement reagent was obtained. Please refer to its XRD pattern Figure 2 The standard sheet used in the XRD test is PDF No.38-1140, and its SEM image can be found in 3.

[0170] Follow the steps below to apply the Li6CoO4 in this example to the ternary material to assemble an all-solid-state battery.

[0171] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary: solid electrolyte: Li6CoO4 lithium supplement reagent: conductive agent = 80:15:4:1 mass ratio. The positive electrode active material loading is 20 mg / cm 2 The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 The solid-state battery was assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge test. The voltage window of battery charge and discharge was 2-4.3V. The cycle test was carried out at 0.33C charge / 0.33C discharge for 50 cycles.

[0172] Embodiment 31

[0173] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0174] Compared with Example 30, the lithium raw material is Li2O, and other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0175] Embodiment 32

[0176] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0177] Compared with Example 30, the lithium raw material is Li2CO3, and other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0178] Embodiment 33

[0179] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0180] Compared with Example 30, the lithium raw material is LiNO3, and other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0181] Embodiment 34

[0182] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0183] Compared with Example 30, the lithium raw material is Li2SO4, and other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0184] Embodiment 35

[0185] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0186] Compared with Example 30, according to the mass ratio of CoO:LiOH=1:0.1, 10g of CoO and 1g of LiOH were weighed respectively; other conditions remained unchanged, and finally Li6CoO4 lithium supplement reagent was obtained. According to the steps in Example 30, the Li6CoO4 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0187] Embodiment 36

[0188] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0189] Compared with Example 30, according to the mass ratio of CoO:LiOH=1:10, 10g of CoO and 100g of LiOH were weighed respectively; other conditions remained unchanged, and finally Li6CoO4 lithium supplement reagent was obtained. According to the steps in Example 30, the Li6CoO4 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0190] Embodiment 37

[0191] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0192] Compared with Example 30, the mixing time is 1 min; other conditions remain unchanged, and finally the Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0193] Embodiment 38

[0194] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0195] Compared with Example 30, the mixing time is 10 minutes; other conditions remain unchanged, and finally the Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0196] Embodiment 39

[0197] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0198] Compared with Example 30, the mixing speed is 200 rpm; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0199] Embodiment 40

[0200] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0201] The heating rate of the first stage of heat treatment is 1°C / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0202] Embodiment 41

[0203] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0204] Compared with Example 30, the heating rate of the first stage of heat treatment is 5°C / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0205] Embodiment 42

[0206] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0207] Compared with Example 30, the temperature of the first stage of heat treatment is 300°C; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0208] Embodiment 43

[0209] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0210] Compared with Example 30, the temperature of the first stage of heat treatment is 700°C; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0211] Embodiment 44

[0212] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0213] Compared with Example 30, the time for the first stage of heat treatment is 2 hours; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0214] Embodiment 45

[0215] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0216] Compared with Example 30, the time for the first stage of heat treatment is 10 hours; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0217] Embodiment 46

[0218] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0219] Compared with Example 30, the air flow rate of compressed air in the first heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0220] Embodiment 47

[0221] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0222] Compared with Example 30, the heating rate of the second heat treatment stage is 3°C / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0223] Embodiment 48

[0224] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0225] Compared with Example 30, the temperature of the second heat treatment stage is 500°C; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0226] Embodiment 49

[0227] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0228] Compared with Example 30, the temperature of the second heat treatment stage is 900°C; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0229] Embodiment 50

[0230] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0231] Compared with Example 30, the time of the second heat treatment stage is 8 hours; other conditions remain unchanged, and finally the Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0232] Embodiment 51

[0233] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0234] Compared with Example 30, the time of the second heat treatment stage is 20 hours; other conditions remain unchanged, and finally the Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0235] Embodiment 52

[0236] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0237] Compared with Example 30, the air flow rate of compressed air in the second heat treatment stage is 3L / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0238] Embodiment 53

[0239] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0240] Compared with Example 30, the air flow rate of compressed air in the second heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0241] Embodiment 54

[0242] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0243] Compared with Example 30, the air flow rate of compressed air in the cooling stage is 5L / min; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0244] Embodiment 55

[0245] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0246] Compared with Example 30, a 200-mesh sieve is used; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0247] Embodiment 56

[0248] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0249] Compared with Example 30, a 400-mesh sieve is used; other conditions remain unchanged, and finally Li6CoO4 lithium supplement reagent is obtained. According to the steps in Example 30, the Li6CoO4 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0250] Embodiment 57

[0251] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0252] Weigh 10g of NiO and 1.8g of Li2O according to the mass ratio of 1:0.18; add them to the mill for 3min at a speed of 800rpm; after mixing evenly, pour the powder into a crucible and transfer it to a muffle furnace for heat treatment. The heat treatment process is as follows: the heating rate of the first heat treatment stage is 4℃ / min, the temperature of the first heat treatment stage is 480℃, and the time of the first heat treatment stage is 7h; the air flow rate of compressed air in the first heat treatment stage is 18L / min; the heating rate of the second heat treatment stage is 4℃ / min, the temperature of the second heat treatment stage is 790℃, the time of the second heat treatment stage is 18h, and the air flow rate of compressed air in the second heat treatment stage is 6L / min; the air flow rate of compressed air in the cooling stage is 1L / min. When the temperature drops to 200℃, quickly transfer it to the glove box, grind it finely, and pass it through a 300-mesh sieve. Finally, the Li2NiO2 lithium supplement reagent is obtained.

[0253] Follow the steps below to apply the LiNiO2 in this embodiment to the ternary material to assemble an all-solid-state battery.

[0254] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary: solid electrolyte: Li2NiO2 lithium supplement reagent: conductive agent = 76:15:8:1 mass ratio. The positive electrode active material loading is 20 mg / cm 2The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 The solid-state battery was assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge test. The voltage window of battery charge and discharge was 2-4.3V. The cycle test was carried out at 0.33C charge / 0.33C discharge for 50 cycles.

[0255] Embodiment 58

[0256] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0257] Compared with Example 57, the lithium raw material is LiOH, and other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0258] Embodiment 59

[0259] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0260] Compared with Example 57, the lithium raw material is Li2CO3, and other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0261] Embodiment 60

[0262] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0263] Compared with Example 57, the lithium raw material is LiNO3, and other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0264] Embodiment 61

[0265] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0266] Compared with Example 57, the lithium raw material is Li2SO4, and other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0267] Embodiment 62

[0268] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0269] Compared with Example 57, according to the mass ratio of NiO:Li2O=1:0.1, 10g of NiO and 1g of Li2O were weighed respectively; other conditions remained unchanged, and finally Li2NiO2 lithium supplement reagent was obtained. According to the steps in Example 57, the Li2NiO2 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0270] Embodiment 63

[0271] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0272] Compared with Example 57, according to the mass ratio of NiO:Li2O=1:10, 10g of NiO and 100g of Li2O were weighed respectively; other conditions remained unchanged, and finally Li2NiO2 lithium supplement reagent was obtained. According to the steps in Example 57, the Li2NiO2 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0273] Embodiment 64

[0274] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0275] Compared with Example 57, the mixing time is 1 min; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0276] Embodiment 65

[0277] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0278] Compared with Example 57, the mixing time is 10 minutes; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0279] Embodiment 66

[0280] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0281] Compared with Example 57, the mixing speed is 200 rpm; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0282] Embodiment 67

[0283] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0284] Compared with Example 57, the mixing speed is 1000 rpm; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0285] Embodiment 68

[0286] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0287] Compared with Example 57, the heating rate of the first stage of heat treatment is 1°C / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0288] Embodiment 69

[0289] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0290] Compared with Example 57, the heating rate of the first stage of heat treatment is 5°C / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0291] Embodiment 70

[0292] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0293] Compared with Example 57, the temperature of the first stage of heat treatment is 300°C; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0294] Embodiment 71

[0295] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0296] Compared with Example 57, the temperature of the first stage of heat treatment is 700°C; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0297] Embodiment 72

[0298] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0299] Compared with Example 57, the time for the first stage of heat treatment is 2 hours; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0300] Embodiment 73

[0301] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0302] Compared with Example 57, the time for the first stage of heat treatment is 10 hours; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0303] Embodiment 74

[0304] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0305] Compared with Example 57, the air flow rate of compressed air in the first heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0306] Embodiment 75

[0307] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0308] Compared with Example 57, the air flow rate of compressed air in the first heat treatment stage is 20 L / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0309] Embodiment 76

[0310] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0311] Compared with Example 57, the heating rate of the second heat treatment stage is 3°C / min; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0312] Embodiment 77

[0313] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0314] Compared with Example 57, the heating rate of the second heat treatment stage is 5°C / min; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0315] Embodiment 78

[0316] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0317] Compared with Example 57, the temperature of the second heat treatment stage is 500°C; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0318] Embodiment 79

[0319] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0320] Compared with Example 57, the temperature of the second heat treatment stage is 900°C; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0321] Embodiment 80

[0322] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0323] Compared with Example 57, the time of the second heat treatment stage is 8 hours; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0324] Embodiment 81

[0325] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0326] Compared with Example 57, the time of the second heat treatment stage is 20 hours; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0327] Embodiment 82

[0328] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0329] Compared with Example 57, the gas flow rate of compressed air in the second heat treatment stage is 3L / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0330] Embodiment 83

[0331] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0332] Compared with Example 57, the air flow rate of compressed air in the second heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0333] Embodiment 84

[0334] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0335] Compared with Example 57, the air flow rate of compressed air in the cooling stage is 5 L / min; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0336] Embodiment 85

[0337] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0338] Compared with Example 57, a 200-mesh sieve is used; other conditions remain unchanged, and finally the Li2NiO2 lithium supplement reagent is obtained. According to the steps in Example 57, the Li2NiO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0339] Embodiment 86

[0340] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0341] Compared with Example 57, a 400-mesh sieve was used; other conditions remained unchanged, and finally the Li2NiO2 lithium supplement reagent was obtained. According to the steps in Example 57, the Li2NiO2 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0342] Embodiment 87

[0343] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0344] CuO and Li2O are weighed at a mass ratio of 1:0.37, 10g of CuO and 3.7g of Li2O are weighed respectively; added to the mill for 4min at a speed of 700rpm; after being evenly mixed, the powder is poured into a crucible and transferred to a muffle furnace for heat treatment. The heat treatment process is as follows: the heating rate of the first heat treatment stage is 3℃ / min, the temperature of the first heat treatment stage is 490℃, the time of the first heat treatment stage is 4h, and the air flow rate of compressed air in the first heat treatment stage is 17L / min; the heating rate of the second heat treatment stage is 5℃ / min, the temperature of the second heat treatment stage is 780℃, the time of the second heat treatment stage is 16h, and the air flow rate of compressed air in the second heat treatment stage is 5L / min; the air flow rate of compressed air in the cooling stage is 1L / min. When the temperature drops to 200℃, quickly transfer it to the glove box, grind it finely, and pass it through a 300-mesh sieve. Finally, the Li2CuO2 lithium supplement reagent is obtained.

[0345] Follow the steps below to apply the Li2CuO2 in this example to the ternary material to assemble an all-solid-state battery.

[0346] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary: solid electrolyte: Li2CuO2 lithium supplement reagent: conductive agent = 76:15:8:1 mass ratio. The positive electrode active material loading is 20 mg / cm 2 The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 The solid-state battery was assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge test. The voltage window of battery charge and discharge was 2-4.3V. The cycle test was carried out at 0.33C charge / 0.33C discharge for 50 cycles.

[0347] Embodiment 88

[0348] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0349] Compared with Example 87, the lithium raw material is LiOH, and other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0350] Embodiment 89

[0351] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0352] Compared with Example 87, the lithium raw material is Li2CO3, and other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0353] Embodiment 90

[0354] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0355] Compared with Example 87, the lithium raw material is LiNO3, and other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0356] Embodiment 91

[0357] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0358] Compared with Example 87, the lithium raw material is Li2SO4, and other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0359] Embodiment 92

[0360] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0361] Compared with Example 87, CuO:Li2O is prepared in a mass ratio of 1:0.1, and 10g of CuO and 1g of Li2O are weighed respectively; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0362] Embodiment 93

[0363] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0364] Compared with Example 87, the CuO:Li2O mass ratio is 1:10, and 10g of CuO and 100g of Li2O are weighed respectively; other conditions remain unchanged, and finally the Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0365] Embodiment 94

[0366] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0367] Compared with Example 87, the mixing time is 1 min; other conditions remain unchanged, and finally the Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0368] Embodiment 95

[0369] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0370] Compared with Example 87, the mixing time is 10 minutes; other conditions remain unchanged, and finally the Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0371] Embodiment 96

[0372] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0373] Compared with Example 87, the mixing speed is 200 rpm; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0374] Embodiment 97

[0375] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0376] Compared with Example 87, the mixing speed is 1000 rpm; finally, Li2CuO2 lithium supplement reagent is obtained, and the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery according to the steps in Example 87.

[0377] Embodiment 98

[0378] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0379] Compared with Example 87, the heating rate of the first stage of heat treatment is 1°C / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0380] Embodiment 99

[0381] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0382] Compared with Example 87, the heating rate of the first stage of heat treatment is 5°C / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0383] Embodiment 100

[0384] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0385] Compared with Example 87, the temperature of the first stage of heat treatment is 300°C; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0386] Embodiment 101

[0387] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0388] Compared with Example 87, the temperature of the first stage of heat treatment is 700°C; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0389] Embodiment 102

[0390] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0391] Compared with Example 87, the time for the first stage of heat treatment is 2 hours; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0392] Embodiment 103

[0393] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0394] Compared with Example 87, the time for the first stage of heat treatment is 10 hours; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0395] Embodiment 104

[0396] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0397] Compared with Example 87, the air flow rate of compressed air in the first heat treatment stage is 10 L / min; finally, Li2CuO2 lithium supplement reagent is obtained, and the Li2CuO2 in this example is applied to the ternary material according to the steps in Example 87 to assemble an all-solid-state battery.

[0398] Embodiment 105

[0399] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0400] Compared with Example 87, the air flow rate of compressed air in the first heat treatment stage is 20 L / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0401] Embodiment 106

[0402] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0403] Compared with Example 87, the heating rate of the second heat treatment stage is 3°C / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0404] Embodiment 107

[0405] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0406] Compared with Example 87, the temperature of the second heat treatment stage is 500°C; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0407] Embodiment 108

[0408] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0409] Compared with Example 87, the temperature of the second heat treatment stage is 900°C; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0410] Embodiment 109

[0411] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0412] Compared with Example 87, the time of the second heat treatment stage is 8 hours; other conditions remain unchanged, and finally the Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0413] Embodiment 110

[0414] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0415] Compared with Example 87, the time of the second heat treatment stage is 20 hours; other conditions remain unchanged, and finally the Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0416] Embodiment 111

[0417] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0418] Compared with Example 87, the air flow rate of compressed air in the second heat treatment stage is 3L / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0419] Embodiment 112

[0420] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0421] Compared with Example 87, the air flow rate of compressed air in the second heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0422] Embodiment 113

[0423] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0424] Compared with Example 87, the air flow rate of compressed air in the cooling stage is 5 L / min; other conditions remain unchanged, and finally Li2CuO2 lithium supplement reagent is obtained. According to the steps in Example 87, the Li2CuO2 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0425] Embodiment 114

[0426] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0427] Compared with Example 87, a 200-mesh sieve was used; other conditions remained unchanged, and finally the Li2CuO2 lithium supplement reagent was obtained. According to the steps in Example 87, the Li2CuO2 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0428] Embodiment 115

[0429] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0430] Compared with Example 87, a 400-mesh sieve was used; other conditions remained unchanged, and finally the Li2CuO2 lithium supplement reagent was obtained. According to the steps in Example 87, the Li2CuO2 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0431] Embodiment 116

[0432] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0433] MnO2 and Li2O are weighed at a mass ratio of 1:0.35, 10g of MnO2 and 3.5g of Li2O are weighed respectively; added to the mill for 3 minutes at a speed of 750rpm; after being evenly mixed, the powder is poured into a crucible and transferred to a muffle furnace for heat treatment. The heat treatment process is as follows: the heating rate of the first heat treatment stage is 3℃ / min, the temperature of the first heat treatment stage is 480℃, the time of the first heat treatment stage is 4h, and the air flow rate of compressed air in the first heat treatment stage is 17L / min; the heating rate of the second heat treatment stage is 5℃ / min, the temperature of the second heat treatment stage is 780℃, the time of the second heat treatment stage is 17h, and the air flow rate of compressed air in the second heat treatment stage is 6L / min; the air flow rate of compressed air in the cooling stage is 1L / min. When the temperature drops to 200℃, quickly transfer it to the glove box, grind it finely, and pass it through a 300-mesh sieve. Finally, Li2MnO3 lithium supplement reagent was obtained.

[0434] Follow the steps below to apply the Li2MnO3 in this example to the ternary material to assemble an all-solid-state battery.

[0435] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary: solid electrolyte: Li2MnO3 lithium supplement reagent: conductive agent = 76:15:8:1 mass ratio. The positive electrode active material loading is 20 mg / cm 2 The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 The solid-state battery was assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge test. The voltage window of battery charge and discharge was 2-4.3V. The cycle test was carried out at 0.33C charge / 0.33C discharge for 50 cycles.

[0436] Embodiment 117

[0437] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0438] Compared with Example 116, the lithium raw material is LiOH, and other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0439] Embodiment 118

[0440] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0441] Compared with Example 116, the lithium raw material is Li2CO3, and other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0442] Embodiment 119

[0443] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0444] Compared with Example 116, the lithium raw material is LiNO3, and other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0445] Embodiment 120

[0446] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0447] Compared with Example 116, the lithium raw material is Li2SO4, and other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0448] Embodiment 121

[0449] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0450] Compared with Example 116, MnO2:Li2O is prepared in a mass ratio of 1:0.1, and 10 g of MnO2 and 1 g of Li2O are weighed respectively; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0451] Embodiment 122

[0452] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0453] Compared with Example 116, MnO2:Li2O is in a mass ratio of 1:10, and 10g of MnO2 and 100g of Li2O are weighed respectively; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0454] Embodiment 123

[0455] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0456] Compared with Example 116, the mixing time is 1 min; other conditions remain unchanged, and finally the Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0457] Embodiment 124

[0458] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0459] Compared with Example 116, the mixing time is 10 minutes; other conditions remain unchanged, and finally the Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0460] Embodiment 125

[0461] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0462] Compared with Example 116, the mixing speed is 200 rpm; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0463] Embodiment 126

[0464] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0465] Compared with Example 116, the mixing speed is 1000 rpm; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0466] Embodiment 127

[0467] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0468] Compared with Example 116, the heating rate of the first stage of heat treatment is 1°C / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0469] Embodiment 128

[0470] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0471] Compared with Example 116, the heating rate of the first stage of heat treatment is 5°C / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0472] Embodiment 129

[0473] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0474] Compared with Example 116, the temperature of the first stage of heat treatment is 300°C; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0475] Embodiment 130

[0476] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0477] Compared with Example 116, the temperature of the first stage of heat treatment is 700°C; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0478] Embodiment 131

[0479] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0480] Compared with Example 116, the time for the first stage of heat treatment is 2 hours; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0481] Embodiment 132

[0482] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0483] Compared with Example 116, the time for the first stage of heat treatment is 10 hours; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0484] Embodiment 133

[0485] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0486] Compared with Example 116, the gas flow rate of compressed air in the first heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0487] Embodiment 134

[0488] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0489] Compared with Example 116, the gas flow rate of compressed air in the first heat treatment stage is 20 L / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0490] Embodiment 135

[0491] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0492] Compared with Example 116, the heating rate of the second heat treatment stage is 3°C / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0493] Embodiment 136

[0494] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0495] Compared with Example 116, the temperature of the second heat treatment stage is 500°C; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0496] Embodiment 137

[0497] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0498] Compared with Example 116, the temperature of the second heat treatment stage is 900°C; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0499] Embodiment 138

[0500] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0501] Compared with Example 116, the time of the second heat treatment stage is 8 hours; other conditions remain unchanged, and finally the Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0502] Embodiment 139

[0503] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0504] Compared with Example 116, the time of the second heat treatment stage is 20 hours; other conditions remain unchanged, and finally the Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0505] Embodiment 140

[0506] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0507] Compared with Example 116, the gas flow rate of compressed air in the second heat treatment stage is 3 L / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0508] Embodiment 141

[0509] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0510] Compared with Example 116, the gas flow rate of compressed air in the second heat treatment stage is 10 L / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0511] Embodiment 142

[0512] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0513] Compared with Example 116, the air flow rate of compressed air in the cooling stage is 5 L / min; other conditions remain unchanged, and finally Li2MnO3 lithium supplement reagent is obtained. According to the steps in Example 116, the Li2MnO3 in this example is applied to the ternary material to assemble an all-solid-state battery.

[0514] Embodiment 143

[0515] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0516] Compared with Example 116, a 200-mesh sieve was used; other conditions remained unchanged, and finally Li2MnO3 lithium supplement reagent was obtained. According to the steps in Example 116, the Li2MnO3 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0517] Embodiment 144

[0518] This example is used to illustrate the preparation method of the lithium supplement, the lithium supplement and the all-solid-state battery of the present invention.

[0519] Compared with Example 116, a 400-mesh sieve was used; other conditions remained unchanged, and finally the Li2MnO3 lithium supplement reagent was obtained. According to the steps in Example 116, the Li2MnO3 in this example was applied to the ternary material to assemble an all-solid-state battery.

[0520] Comparative Example 1

[0521] No lithium supplement reagent is added when assembling the all-solid-state battery, as follows:

[0522] The mass of the electrolyte layer is 150 mg. The positive electrode is prepared by grinding and mixing the ternary material: solid electrolyte: conductive agent in a mass ratio of 85:14:1. The positive electrode active material loading is 20 mg / cm 2 The negative electrode was prepared by grinding and mixing graphite and solid electrolyte in a mass ratio of 60:40, and the negative electrode active material loading was 17 mg / cm 2 The solid-state battery was assembled in the order of positive electrode / electrolyte layer / negative electrode for charge and discharge test. The voltage window of battery charge and discharge was 2-4.3V. The cycle test was carried out at 0.33C charge / 0.33C discharge for 50 cycles.

[0523] The charge and discharge test data of the solid-state batteries of the above embodiments and comparative examples are shown in Table 1. Table 1 is the charge and discharge test results of the all-solid-state batteries of the embodiments and comparative examples.

[0524] Table 1. Charge and discharge test results of all-solid-state batteries of the embodiments and comparative examples

[0525]

[0526]

[0527]

[0528]

[0529]

[0530] Through the above comparison, the reduction in the first cycle coulombic efficiency of the embodiment is mainly caused by the irreversible charge and discharge behavior of the lithium replenishing agent. In the subsequent 50 cycles, it can be observed that the cycle performance of the ternary material after adding the lithium replenishing agent has been greatly improved, and the retention rate is more than 90%, while the retention rate of the ternary material without adding the lithium replenishing agent is less than 80%. The main reason for the significant improvement in the cycle performance of the ternary material with the addition of the lithium replenishing agent is that the lithium source consumed by the formation of the interface SEI film is compensated during the cycle.

[0531] It can be seen from the above technical scheme of the embodiment of the present invention that the present invention discloses a method for preparing a lithium supplement, which comprises: providing raw materials; wherein the raw materials comprise a metal oxide raw material with a stable valence state and a lithium raw material; mixing the raw materials to obtain a first intermediate product; and heat-treating the first intermediate product in a flowing compressed air atmosphere to obtain a lithium supplement. By using a metal oxide with a stable valence state as a raw material, it has high stability at high temperatures, avoids redox side reactions in an air environment, avoids the use of inert gas as a protective gas, thereby reducing the preparation cost, and the obtained lithium supplement has excellent lithium supplement performance, thereby improving the energy density and cycle performance of the all-solid-state battery based on the lithium supplement.

[0532] The above description has fully disclosed the specific embodiments of the present invention. It should be pointed out that any changes made by those skilled in the art to the specific embodiments of the present invention do not deviate from the scope of the claims of the present invention. Accordingly, the scope of the claims of the present invention is not limited to the above specific embodiments.

Claims

1. A method for preparing a lithium supplement, characterized in that: The method comprises: Providing raw materials; the raw materials include metal oxide raw materials with stable valence and lithium raw materials; mixing the raw materials to obtain a first intermediate product; The first intermediate product is heat-treated under a flowing compressed air atmosphere to obtain the lithium supplement agent.

2. The method according to claim 1, characterized in that The heat treatment includes a first heat treatment stage, a second heat treatment stage and a temperature reduction stage; The heating rate of the first heat treatment stage is 1-5°C / min, the temperature of the first heat treatment stage is 300-700°C, the time of the first heat treatment stage is 2-10h, and the air flow rate of the compressed air in the first heat treatment stage is 10-20L / min; The heating rate of the second heat treatment stage is 3-5°C / min, the temperature of the second heat treatment stage is 500-900°C, the time of the second heat treatment stage is 8-20h, and the air flow rate of the compressed air in the second heat treatment stage is 3-10L / min; The air flow rate of the compressed air in the cooling stage is 1 to 5 L / min.

3. The method according to claim 1, characterized in that The metal oxide raw material with stable valence state includes one or more combinations of Fe2O3, CuO, NiO, MnO2 or CoO.

4. The method according to claim 1, characterized in that: The lithium raw material includes one or more combinations of Li2O, LiOH, Li2CO3, LiNO3 or Li2SO4.

5. The method according to claim 1, characterized in that The mass ratio of the metal oxide raw material in a stable valence state to the lithium raw material is 1:(0.1-10).

6. The method according to claim 1, characterized in that The mixing of the raw materials to obtain the first intermediate product comprises: Using a grinding mill, mixing the raw materials to obtain the first intermediate product; The mixing time is 1 to 10 minutes, and the mixing speed is 200 to 1000 rpm.

7. The method according to claim 1, characterized in that The step of heat treating the first intermediate product under a flowing compressed air atmosphere to obtain the lithium supplement comprises: Under the flowing compressed air atmosphere, heat-treating the first intermediate product to obtain a second intermediate product; Refining the second intermediate product to obtain a third intermediate product; The third intermediate product is screened to obtain the lithium supplement agent.

8. The method according to claim 7, characterized in that The screening of the third product to obtain the lithium supplement comprises: The third intermediate product is sieved using a sieve to obtain the lithium supplement; the mesh size of the sieve ranges from 200 to 400 meshes.

9. A lithium supplement, characterized in that: A lithium supplement prepared by the method according to any one of claims 1 to 8.

10. An all-solid-state battery, characterized in that: Including the lithium supplement described in claim 9.

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