Lithium ion sieve adsorbent material and preparation method therefor and use thereof

Abstract

Provided are a lithium ion sieve adsorbent material and a preparation method therefor and a use thereof, relating to the technical field of energy materials. The chemical formula of the lithium ion sieve adsorbent material is M1y(LixM21-x)O2, wherein M1 is selected from at least one of non-lithium alkali metal elements, M2 is selected from at least one of transition metal elements, and Li and the transition metal element M2 share one lattice position. The preparation method for the lithium ion sieve adsorbent material is a novel method, the usage amount of the lithium source in the raw materials is only 50% or less of that of the lithium source of traditional adsorbent materials, a pickling removal procedure is not needed, the industrial process is simple, and the production cost is low; the prepared lithium ion sieve has high purity and high adsorption capacity; the adsorbent can adsorb lithium ions in a solution, and the material after lithium ion adsorption can also be used as a raw material for preparing a lithium ion electrode material, thereby expanding raw material sources of lithium ion electrode materials; and the adsorbent has wide application prospects in the field of new energy.

Description

A lithium ion sieve adsorbent material and its preparation method and application Technical Field

[0001] The present invention belongs to the technical field of energy materials, and in particular relates to a lithium ion sieve adsorbent material and a preparation method and application thereof. Background Art

[0002] Lithium is widely used in energy, electronics, chemicals, aerospace, and other fields. Currently, approximately three-quarters of the world's lithium resources are used to manufacture lithium-ion batteries. With the growth of the new energy vehicle and energy storage industries, the demand for lithium-ion batteries and lithium resources is also increasing. Salt lake brines contain vast amounts of lithium resources, accounting for approximately 60% of the world's lithium resources. Efficiently extracting lithium from these brines has become a pressing issue.

[0003] In terms of lithium extraction from salt lake brine, the adsorbent method, solvent extraction method, membrane method, etc. are the main methods. Among them, the adsorption method is considered to be one of the most promising methods for lithium extraction from salt lakes due to its good ion selectivity, environmental friendliness, and high recycling rate. The core of the adsorption method is the adsorbent material, among which ion sieve type oxides are the most studied and best performing adsorbents. Existing ion sieve adsorbents mainly include aluminum, manganese and titanium series, especially spinel manganese series (HMn2O4, H 1.33 Mn 1.67 O4、H 1.6 Mn 1.6 O4, etc.) and titanium-based ion sieve materials (H2TiO3, etc.) have the characteristics of good selectivity, large adsorption capacity and high recycling rate, which can significantly improve the efficiency of lithium extraction from brine.

[0004] However, traditional lithium ion sieve materials require a lithium source (such as lithium hydroxide or lithium carbonate) as a raw material. First, a lithium-containing precursor is prepared, and then the lithium in the lattice is washed away by dilute sulfuric acid or dilute hydrochloric acid to obtain the ion sieve material. Not only is the process complicated and costly, but it also consumes a large amount of fresh water and acid, causing serious pollution. In the subsequent use process, traditional lithium ion sieve materials use the working principle of proton-lithium ion exchange to extract lithium from brine, and are recycled through acid elution, which has problems such as insufficient stability.

[0005] Summary of the Invention

[0006] In view of this, the present invention provides a lithium ion sieve adsorbent material and its preparation method and application, the main purpose of which is to solve the technical problems of large lithium source consumption in the synthetic raw materials of lithium ion sieve adsorbent, complex preparation process and serious pickling pollution.

[0007] In one aspect, the present invention provides a lithium ion sieve adsorbent material, wherein the chemical formula of the lithium ion sieve adsorbent material is Formula I; M1 y (Lix M2 1-x )O2 Formula I;

[0008] M1 in Formula I is selected from at least one of non-lithium alkali metal elements, <y≤1;

[0009] M2 in Formula I is selected from at least one transition metal element;

[0010] Li and the transition metal element M2 occupy one lattice position, 0≤x<0.5.

[0011] In the above formula I of the present invention, x and y represent the molar ratio of the corresponding metal elements.

[0012] Optionally, y in Formula I is selected from any value selected from 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, or any range therebetween.

[0013] Optionally, x in Formula I is selected from any value among 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.49, or any range between two thereof.

[0014] During the research and development of lithium ion adsorbents, the inventors discovered that traditional lithium ion sieve adsorbents require a large amount of lithium source as the raw material of the molecular sieve during the preparation process. It is necessary to first prepare a lithium-containing precursor, and then remove the lithium in the molecular sieve lattice through an acid washing process to obtain the lithium ion sieve adsorbent material. In this method, a large amount of lithium source is used, which increases production costs, and the pickling water seriously pollutes the environment. In response to the above problems, the inventors have innovatively proposed how to reduce the amount of lithium source used and not use the pickling process to still prepare a lithium ion sieve adsorbent material with high purity, high adsorption capacity and good stability. In order to solve the above technical problems, the inventors have proposed for the first time a lithium ion sieve adsorbent material, which has a different elemental composition and a different working principle compared with traditional adsorbents. Specifically, the present invention innovatively introduces non-lithium alkali metal M1 into the elemental composition of the lithium ion sieve adsorbent, and utilizes the working principle that the non-lithium alkali metal M1 can spontaneously exchange ions with lithium ions in a lithium-containing solution, thereby achieving the purpose of the lithium ion sieve adsorbent material being able to adsorb lithium ions in a lithium-containing solution, thereby achieving the purpose of preparing a lithium ion sieve adsorbent material with high purity, high adsorption capacity and good stability under the conditions of reducing the amount of lithium source used (the amount of lithium source used in the present invention is less than 50% of the lithium source of the traditional adsorbent material) and not using the pickling process.

[0015] Optionally, M1 in Formula I is selected from at least one of non-lithium alkali metal elements Na, K, Rb and Cs.

[0016] Optionally, M2 in Formula I is selected from at least one of transition metal elements Fe, Co, Ni and Mn.

[0017] The non-lithium alkali metal ions in the above-mentioned lithium ion sieve adsorbent material of the present invention spontaneously exchange ions with the lithium ions in the solution, thereby achieving the purpose of the molecular sieve material containing the transition metal system being able to adsorb lithium ions in the solution; the function of the lithium ion sieve adsorbent of the present invention is mainly achieved by the composite of the non-lithium alkali metal element M1 and the transition metal element M2, and the compound of the composite metal can be selected from its oxide to achieve the purpose of adsorbing lithium ions in the solution.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned lithium ion sieve adsorbent material, comprising the following steps:

[0019] S1: mixing a non-lithium alkali metal source, a lithium source, and a transition metal source to obtain a mixture;

[0020] S2: The mixture is subjected to high-temperature solid-phase sintering and then cooled to obtain a lithium ion sieve adsorbent material.

[0021] The present invention introduces a non-lithium alkali metal source into the raw materials of the above preparation method, which can reduce the amount of lithium source used, does not require an acid washing process, simplifies the preparation process, and reduces production costs.

[0022] Optionally, in step S1, the molar ratio of the non-lithium alkali metal source to the transition metal source is 0.3 to 2:1.

[0023] Optionally, the molar ratio of the non-lithium alkali metal source to the transition metal source is selected from any value among 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 or any range value therebetween.

[0024] Optionally, in step S1, the molar ratio of the lithium source to the transition metal source is 0 to 0.3:1.

[0025] Optionally, the molar ratio of the lithium source to the transition metal source is any value among 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, or any range between two values.

[0026] Optionally, in step S1, the lithium source is selected from at least one of lithium oxide, lithium carbonate, lithium oxalate, lithium acetate and lithium hydroxide;

[0027] The sodium source in the non-lithium alkali metal source is selected from at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium acetate and sodium hydroxide;

[0028] The potassium source in the non-lithium alkali metal source is selected from at least one of potassium oxide, potassium carbonate, potassium oxalate, potassium acetate and potassium hydroxide;

[0029] The rubidium source in the non-lithium alkali metal source is selected from at least one of rubidium oxide, rubidium carbonate, rubidium oxalate, rubidium acetate and rubidium hydroxide;

[0030] The cesium source in the non-lithium alkali metal source is selected from at least one of cesium oxide, cesium carbonate, cesium oxalate, cesium acetate and cesium hydroxide;

[0031] The iron source in the transition metal source is selected from at least one of iron oxide, iron carbonate, iron oxalate, iron acetate and iron hydroxide;

[0032] The cobalt source in the transition metal source is selected from at least one of cobalt oxide, cobalt carbonate, cobalt oxalate, cobalt acetate and cobalt hydroxide;

[0033] The nickel source in the transition metal source is selected from at least one of nickel oxide, nickel carbonate, nickel oxalate, nickel acetate and nickel hydroxide;

[0034] The manganese source in the transition metal source is selected from at least one of manganese oxide, manganese carbonate, manganese oxalate, manganese acetate and manganese hydroxide.

[0035] Optionally, in step S1, the non-lithium alkali metal source, the lithium source and the transition metal source are mixed by at least one of manual grinding, ball milling, solution evaporation and co-precipitation.

[0036] Optionally, in step S2, the temperature of the high-temperature solid-phase sintering is 500° C. to 1000° C., and the time of the high-temperature solid-phase sintering is 0.5 h to 24 h.

[0037] Preferably, the temperature of the high-temperature solid-phase sintering is 500° C. to 850° C., and the time of the high-temperature solid-phase sintering is 0.5 h to 6 h.

[0038] Further preferably, the temperature of the high-temperature solid-phase sintering is 500°C to 700°C.

[0039] Optionally, the temperature of the high-temperature solid-phase sintering is selected from any value of 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C or any range between two values.

[0040] Optionally, the time of the high temperature solid phase sintering is selected from any value among 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h, 23.5h, 24h, or any range between two of them.

[0041] Optionally, the cooling in step S2 is natural cooling to room temperature.

[0042] In a third aspect, the present invention provides an application of the lithium ion sieve adsorbent material in adsorbing lithium ions in a lithium-containing solution; the non-lithium alkali metal ions M1 in the lithium ion sieve adsorbent material spontaneously undergo ion exchange with the lithium ions in the lithium-containing solution.

[0043] Optionally, the lithium-containing solution includes salt lake brine, mother liquor from lithium extraction and precipitation from ore, lithium-containing waste liquid, lithium-containing solution generated in lithium-ion battery recovery, and their respective purified high-lithium-containing solutions.

[0044] Optionally, the salt lake is a salt lake of various types such as plateau salt lake.

[0045] Optionally, the lithium ion sieve adsorbent material can be mixed with other materials and used as filler in an adsorption tower to extract lithium ions from raw brine or old brine in salt lakes.

[0046] The lithium ion sieve adsorbent material of the present invention can be applied to any type or composition of lithium ion-containing solution, and can achieve the purpose of adsorbing lithium ions.

[0047] In a fourth aspect, the present invention provides the application of the above-mentioned lithium ion sieve adsorbent material in energy storage materials.

[0048] Optionally, after the lithium ion sieve adsorbent material adsorbs lithium ions, it is directly used as one of the raw materials for synthesizing lithium ion battery positive electrode materials.

[0049] After adsorbing lithium ions, the lithium ion sieve adsorbent material of the present invention forms a new material of a transition metal compound containing a large amount of lithium ions.

[0050] The present invention is based on a new lithium ion material formed after the above-mentioned lithium ion sieve adsorption material adsorbs lithium ions. Taking into full consideration the application value of the large amount of lithium ions contained in the new lithium ion material, it is innovatively proposed that the new lithium ion material can be applied to the energy storage or power field, and is particularly suitable for use in the positive electrode material of lithium ion batteries.

[0051] In a fifth aspect, the present invention provides the application of the above-mentioned lithium ion material in energy storage materials.

[0052] Optionally, the above lithium ion materials can be directly used as raw materials to prepare positive electrode materials of transition metal oxides for lithium ion batteries.

[0053] In a sixth aspect, the present invention provides a positive electrode material for a lithium-ion battery, wherein the raw materials of the positive electrode material include the above-mentioned lithium-ion material.

[0054] Optionally, the positive electrode material includes a lithium-ion battery ternary positive electrode material, such as Li(Ni, Co, Mn)O2, etc.

[0055] Optionally, the positive electrode material includes a lithium-ion battery manganese-based material, such as LiMn2O4.

[0056] Optionally, the positive electrode material includes lithium cobalt oxide material for lithium-ion batteries.

[0057] The present invention includes at least the following innovative technologies:

[0058] (1) The molecular formula of the lithium ion sieve adsorbent material of the present invention is M1 y (Li x M2 1-x )O2; it has a different elemental composition and working principle from traditional lithium ion sieve adsorbent materials.

[0059] (2) During the preparation process of the lithium ion sieve adsorbent material of the present invention, the lithium source used is more than half less than that of the traditional adsorbent material, and it can be prepared by only one sintering step without the need for an acid washing process.

[0060] (3) The lithium ion sieve adsorbent material of the present invention can be used to adsorb lithium ions in a solution.

[0061] (4) The lithium ion sieve adsorbent material of the present invention absorbs lithium ions in the solution to form new lithium ion materials, which can be used in the field of energy storage, and in particular can be directly used as a raw material to prepare lithium battery positive electrode materials.

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] (1) The amount of lithium source used as a raw material of the lithium ion sieve adsorbent material of the present invention is less than 50% of the amount of lithium source used in traditional adsorbent materials, thereby reducing costs.

[0064] (2) The method for preparing the lithium ion sieve adsorbent material of the present invention is a brand-new method. This method adopts one-step sintering and does not require acid treatment, which can reduce costs, does not consume fresh water and acid, and is environmentally friendly.

[0065] (3) The lithium ion sieve adsorbent material of the present invention has excellent lithium ion selectivity and a high lithium absorption capacity (30-40 mg / g), and can be used for direct extraction of lithium from salt lakes using raw brine, and has good application prospects.

[0066] (4) After adsorbing lithium ions, the lithium ion sieve adsorbent material of the present invention can be directly used to prepare high-performance lithium ion battery positive electrode materials without the need for delithiation, thereby avoiding the consumption of fresh water and acid during the delithiation process and realizing truly green lithium extraction and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] FIG1 is an X-ray powder diffraction pattern of a multi-component lithium ion sieve adsorbent material prepared in Example 1 of the present invention;

[0068] FIG2 is a scanning electron microscope image of the multi-component lithium ion sieve adsorbent material prepared in Example 1 of the present invention;

[0069] FIG3 is an X-ray powder diffraction pattern of the ternary cathode material prepared in Example 1 of the present invention;

[0070] FIG4 is a first cycle charge and discharge curve diagram of the ternary cathode material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0071] The following is a clear and complete description of 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 efforts are within the scope of protection of the present invention.

[0072] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0073] The following Examples 1 to 4 were used to prepare the compound represented by Formula I; M1 y (Li x M2 1-x )O2 Formula I;

[0074] M1 in Formula I is selected from at least one of non-lithium alkali metal elements, <y≤1。

[0075] M2 is selected from at least one transition metal element;

[0076] Li and transition metal element M2 occupy one lattice site, 0≤x<0.5;

[0077] x and y represent the molar ratio between the corresponding metal elements.

[0078] Example 1

[0079] Preparation of adsorbent: Weigh 0.370g of analytically pure lithium carbonate, 4.597g of manganese carbonate, 1.059g of sodium carbonate and 2.073g of potassium carbonate, mix and grind them in a mortar for 2 hours, transfer them to a corundum crucible, and heat them to 700℃ at a rate of 10℃ / min in a box-type muffle furnace. Keep the temperature for 10 hours and cool it naturally to room temperature to obtain a lithium ion sieve type compound. Its X-ray diffraction pattern is shown in Figure 1, and its scanning electron microscope image is shown in Figure 2. The molecular formula of the lithium ion sieve adsorbent is (Na 0.4 K 0.6 )(Li 0.2 Mn 0.8 )O2.

[0080] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 200 mg / L. After 8 hours, adsorption equilibrium was reached, and the equilibrium adsorption capacity was measured to be 30.8 mg / g.

[0081] The equilibrium adsorption capacity refers to the ratio of the mass of lithium ions reduced in the adsorption solution to the mass of the adsorbent after the adsorption reaches equilibrium.

[0082] The mass of lithium ions reduced = (initial concentration of lithium ions in the solution - concentration of lithium ions after adsorption equilibrium) × volume of the solution.

[0083] Preparation of the positive electrode material: Weigh 0.611g of the adsorbent material (after adsorption of lithium ions), 0.747g of nickel oxide, 0.321g of cobalt tetroxide, and 0.517g of lithium carbonate. Ball mill the mixture at 400 rpm for 12 hours, sinter at 900°C for 12 hours, and cool to obtain the nickel-cobalt-manganese ternary positive electrode material, Li(Ni,Co,Mn)O2. Its X-ray diffraction pattern is shown in Figure 3, and the first cycle charge-discharge curve is shown in Figure 4.

[0084] Example 2

[0085] Preparation of adsorbent: weigh 0.370 g of analytical pure lithium carbonate, (Ni 0.5 Co 0.2 Mn 0.3)CO3 10.586g, sodium carbonate 2.118g and potassium carbonate 4.146g were ball milled in a ball mill at 400rpm for 10 hours, transferred to a corundum crucible, and heated to 750℃ at a rate of 10℃ / min in a box muffle furnace, kept warm for 10 hours, and naturally cooled to room temperature to obtain a lithium ion sieve type compound; the molecular formula of the lithium ion sieve adsorbent is (Na 0.4 K 0.6 )(Li 0.1 Ni 0.45 Co 0.18 Mn 0.27 )O2.

[0086] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 100 mg / L. After 8 hours, adsorption equilibrium was reached, and the equilibrium adsorption capacity was measured to be 33.5 mg / g.

[0087] Example 3

[0088] Preparation of adsorbent: Add 2.213g of potassium acetate, 4.159g of nickel sulfate hexahydrate, 1.004g of manganese sulfate tetrahydrate and 0.235g of lithium acetate dihydrate to 100mL of deionized water and stir thoroughly to dissolve. The solution was evaporated to dryness in an 80-degree oven, the powder was placed in a corundum crucible, transferred to a muffle furnace, and continued to heat to 800°C at a rate of 5°C / min and kept warm for 10 hours. Then, it was naturally cooled to room temperature to obtain a lithium ion sieve compound; the molecular formula of the lithium ion sieve adsorbent is K(Li 0.1 Ni 0.7 Mn 0.2 )O2.

[0089] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 150 mg / L. After 8 hours, adsorption equilibrium is reached, and the equilibrium adsorption capacity is measured to be 37.4 mg / g.

[0090] Example 4

[0091] Preparation of adsorbent: weigh 0.740 g of analytical pure lithium carbonate, (Ni 0.5 Co 0.2 Mn 0.3 )(OH)2 7.330g, sodium carbonate 3.177g and potassium carbonate 2.764g were ball-milled at 400rpm for 10 hours, transferred to a corundum crucible, and heated to 750℃ at a rate of 10℃ / min in a box muffle furnace, kept warm for 10 hours, and naturally cooled to room temperature to obtain a lithium ion sieve type adsorbent compound; the adsorbent molecular formula is (Na 0.6 K 0.4 )(Li 0.2 Ni0.4 Co 0.16 Mn 0.24 )O2.

[0092] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 100 mg / L. After 8 hours, adsorption equilibrium is reached, and the equilibrium adsorption capacity is measured to be 36.5 mg / g.

[0093] Comparative Example 1

[0094] Preparation of adsorbent: Weigh 0.739 g of analytically pure lithium carbonate and 4.597 g of manganese carbonate, mix and grind them in a mortar for 2 hours, transfer them to a corundum crucible, and heat them to 800°C at a rate of 10°C / min in a box muffle furnace. Keep warm for 10 hours and cool them naturally to room temperature to obtain LiMn2O4, a precursor of a traditional lithium ion sieve compound (HMn2O4); add the precursor to 300 mL of 0.1 mol / L dilute hydrochloric acid, stir at room temperature for 6 hours to complete the acid washing process, filter and dry at 80°C to obtain a traditional lithium ion sieve compound HMn2O4.

[0095] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 200 mg / L. After 8 hours, adsorption equilibrium was reached, and the equilibrium adsorption capacity was measured to be 15.8 mg / g.

[0096] Comparative Example 2

[0097] Preparation of adsorbent: Weigh 1.200g of analytically pure lithium hydroxide and 3.518g of manganese oxyhydroxide, add them to a 50mL hydrothermal tank containing 20ml of deionized water, keep them at 120℃ for 1 day, filter, wash and dry to obtain the intermediate product LiMnO2. Place LiMnO2 in a box-type muffle furnace, heat it to 600℃ at a rate of 10℃ / min, keep it at that temperature for 4 hours, and cool it naturally to room temperature to obtain the traditional lithium ion sieve compound (H 1.6 Mn 1.6 O4) precursor Li 1.6 Mn 1.6 The precursor was added to 2L 0.5mol / L dilute hydrochloric acid and stirred at room temperature for 24 hours to complete the acid washing process. After filtration, it was dried at 60℃ to obtain the traditional lithium ion sieve compound H 1.6 Mn 1.6 O4.

[0098] Adsorption of lithium ions in solution: Weigh 0.5 g of lithium ion sieve adsorbent material and place it in 400 mL of a solution with a lithium ion concentration of 200 mg / L. After 8 hours, adsorption equilibrium was reached, and the equilibrium adsorption capacity was measured to be 28.2 mg / g.

[0099] Examples 1 to 4 of the present invention all successfully prepared lithium ion sieve adsorbent materials; when the adsorbent material was used to adsorb lithium ions in the solution, its adsorption effect was obvious; the new material after the adsorbent adsorbed lithium ions was successfully used to prepare a positive electrode material with good charge and discharge performance.

[0100] The present invention takes the lithium ion sieve adsorbent material prepared in Example 1 as an example, and the adsorbent molecular formula is: (Na 0.4 K 0.6 )(Li 0.2 Mn 0.8 )O2; its structure is shown in the X-ray powder diffraction pattern in Figure 1, and the microscopic morphology of the adsorbent particle surface is shown in the scanning electron microscope image in Figure 2.

[0101] The X-ray diffraction patterns of Examples 2 to 4 of the present invention are similar to FIG1 . Analysis shows that the lithium ion sieve adsorbent materials of Examples 2 to 4 have the following molecular formula structures: (Na 0.4 K 0.6 )(Li 0.1 Ni 0.45 Co 0.18 Mn 0.27 )O2, K(Li 0.1 Ni 0.7 Mn 0.2 )O2, (Na 0.6 K 0.4 )(Li 0.2 Ni 0.4 Co 0.16 Mn 0.24 )O2;

[0102] The lithium ion sieve adsorbent material prepared by the present invention has the following chemical formula: M1 y (Li x M2 1-x )O2;

[0103] Wherein, M1 is selected from at least one of non-lithium alkali metal elements, <y≤1;

[0104] M1 is preferably at least one of the alkali metal elements Na, K, Rb and Cs;

[0105] M2 is selected from at least one transition metal element, preferably at least one of Fe, Co, Ni and Mn; Li and the transition metal element M2 occupy a lattice position, 0≤x<0.5; x and y represent the molar ratio between the corresponding metal elements.

[0106] The present invention takes the lithium ion sieve adsorbent material prepared in Example 1 as an example. The charge and discharge curve of the positive electrode material prepared by using the material after the adsorbent adsorbs lithium ions in the solution is shown in Figure 4, indicating that the positive electrode material prepared by the adsorbent in Example 1 of the present invention after adsorbing lithium ions has good electrical properties.

[0107] The charge and discharge curves of Examples 2-4 of the present invention are similar to Figure 4. The analysis shows that the positive electrode materials prepared after the lithium ion sieve adsorbent materials of Examples 2-4 adsorb lithium ions have good charge and discharge performance; this shows that the new material obtained by the lithium ion adsorbent material of the present invention after adsorbing lithium ions can be used as one of the raw materials to successfully prepare a lithium ion battery positive electrode material with good electrical properties.

[0108] The above experiments and their results show that the lithium ion sieve adsorbent material provided by the present invention and the new lithium ion material formed after adsorbing lithium ions can be used in the field of energy storage or power, especially in the preparation of positive electrode materials for lithium ion batteries.

[0109] In the preparation of lithium ion sieve adsorbent materials in Examples 1 to 4 of the present invention, the proportion of lithium source used in the total amount of raw materials is approximately 4.5wt%, 2.1wt%, 3.1wt% and 5.2wt%, respectively; the proportion of lithium source used in Comparative Examples 1 and 2 in the total amount of raw materials is approximately 13.8wt% and 25.4wt%, respectively; by comparison, it can be seen that the amount of lithium source used in the lithium ion sieve adsorbent material prepared by the method of the present invention is approximately 0.08-0.38 times the amount of lithium source used in the traditional method, which is much less than the amount of lithium source used in the methods of Comparative Examples 1 and 2.

[0110] In the preparation methods of Comparative Examples 1 and 2, the lithium source and the manganese source are mixed and calcined to obtain only the precursor of the adsorbent such as LiMn2O4, Li 1.6 Mn 1.6 O4, the precursor cannot be used to adsorb lithium ions in the solution, and it must be washed with a large amount of hydrochloric acid for 6 or 24 hours to obtain the traditional lithium ion sieve compounds HMn2O4, H 1.6 Mn 1.6 O4, and then use HMn2O4, H 1.6 Mn 1.6 O4 absorbs lithium ions in the solution. This traditional method requires a large amount of lithium source and acid washing, which produces wastewater and is unfriendly to the environment. The preparation method is relatively complicated and the cost is relatively high.

[0111] The method for preparing the lithium ion sieve adsorbent material in Examples 1 to 4 of the present invention is as follows:

[0112] S1: A non-lithium alkali metal source, a lithium source, and a transition metal source are mixed to obtain a mixture;

[0113] S2: The mixture is subjected to high-temperature solid-phase sintering and then cooled to obtain a lithium ion sieve adsorbent material.

[0114] Preferably, the molar ratio of the non-lithium alkali metal source to the transition metal source is 0.3 to 2:1.

[0115] Preferably, the molar ratio of the lithium source to the transition metal source is 0 to 0.3:1.

[0116] As can be seen from Examples 1-4 and Comparative Examples 1-2, the present invention significantly reduces the amount of lithium source used by introducing a non-lithium alkali metal source into the raw materials of the preparation method. Furthermore, the acid washing process is not required, which simplifies the preparation process and directly reduces production costs. Therefore, the preparation method of the present invention has very significant technical effects compared to conventional technologies.

[0117] The adsorption capacities of the lithium ion sieve adsorbent materials prepared in Examples 1-4 of the present invention were 30.8 mg / g, 33.5 mg / g, 37.4 mg / g, and 36.5 mg / g, respectively. Under essentially the same test conditions, the adsorbents prepared using conventional methods in Comparative Examples 1 and 2 had adsorption capacities of 15.8 mg / g and 28.2 mg / g, respectively. This comparison reveals that the adsorbents of the present invention adsorb approximately 1.5-2 times the lithium ion adsorption capacities of the adsorbents of Comparative Examples 1 and 2, demonstrating a stronger lithium ion adsorption capacity. Furthermore, the lithium ion adsorbents of the present invention are recyclable.

[0118] The lithium ion adsorbent material prepared by the new preparation method and reasonable raw material ratio provided by the present invention has lithium ion adsorption capacity and electrical properties.

[0119] The lithium ion sieve adsorbent material provided by the present invention has the advantages of stable structure and large adsorption capacity. After adsorbing lithium ions, the adsorbent material can be directly used to prepare the positive electrode material of lithium ion batteries. The positive electrode material has good electrical properties, which provides a new material for the energy storage field.

[0120] The preparation method of the lithium ion sieve adsorbent material provided by the present invention is easy to operate, greatly reduces the amount of lithium source used, and eliminates the acid washing process, thereby improving production efficiency, reducing production costs, and being environmentally friendly. The preparation method of the present invention expands the source of raw materials for new energy materials, especially lithium battery electrode materials, and has great industrial prospects.

[0121] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A lithium ion sieve adsorbent material, characterized in that: The chemical formula of the lithium ion sieve adsorbent material is Formula I; M1 y (Li x M2 1-x )O2 Formula I; M1 in Formula I is selected from at least one of non-lithium alkali metal elements; <y≤1; M2 in Formula I is selected from at least one transition metal element; Li and the transition metal element M2 occupy one lattice position, 0≤x<0.

5.

2. A lithium ion sieve adsorbent material according to claim 1, characterized in that: M1 in the formula I is selected from at least one of non-lithium alkali metal elements Na, K, Rb and Cs; M2 in the formula I is selected from at least one of transition metal elements Fe, Co, Ni and Mn.

3. The method for preparing a lithium ion sieve adsorbent material according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: S1: A non-lithium alkali metal source, a lithium source, and a transition metal source are mixed to obtain a mixture; S2: The mixture is subjected to high-temperature solid-phase sintering and then cooled to obtain a lithium ion sieve adsorbent material.

4. The method for preparing a lithium ion sieve adsorbent material according to claim 3, characterized in that: In step S1, the molar ratio of the non-lithium alkali metal source to the transition metal source is 0.3-2:1; and the molar ratio of the lithium source to the transition metal source is 0-0.3:

1.

5. The method for preparing a lithium ion sieve adsorbent material according to claim 3, characterized in that: The lithium source is selected from at least one of lithium oxide, lithium carbonate, lithium oxalate, lithium acetate and lithium hydroxide; The sodium source in the non-lithium alkali metal source is selected from at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium acetate and sodium hydroxide; The potassium source in the non-lithium alkali metal source is selected from at least one of potassium oxide, potassium carbonate, potassium oxalate, potassium acetate and potassium hydroxide; The rubidium source in the non-lithium alkali metal source is selected from at least one of rubidium oxide, rubidium carbonate, rubidium oxalate, rubidium acetate and rubidium hydroxide; The cesium source in the non-lithium alkali metal source is selected from at least one of cesium oxide, cesium carbonate, cesium oxalate, cesium acetate and cesium hydroxide; The iron source in the transition metal source is selected from at least one of iron oxide, iron carbonate, iron oxalate, iron acetate and iron hydroxide; The cobalt source in the transition metal source is selected from at least one of cobalt oxide, cobalt carbonate, cobalt oxalate, cobalt acetate and cobalt hydroxide; The nickel source in the transition metal source is selected from at least one of nickel oxide, nickel carbonate, nickel oxalate, nickel acetate and nickel hydroxide; The manganese source in the transition metal source is selected from at least one of manganese oxide, manganese carbonate, manganese oxalate, manganese acetate and manganese hydroxide.

6. The method for preparing a lithium ion sieve adsorbent material according to claim 3, characterized in that: In step S1, the non-lithium alkali metal source, the lithium source and the transition metal source are mixed by at least one of manual grinding, ball milling, solution evaporation and co-precipitation.

7. The method for preparing a lithium ion sieve adsorbent material according to claim 3, characterized in that: In step S2, the temperature of the high-temperature solid-phase sintering is 500°C to 1000°C, and the time of the high-temperature solid-phase sintering is 0.5h to 24h.

8. Use of the lithium ion sieve adsorbent material according to claim 1 or 2 or the lithium ion sieve adsorbent material prepared by the preparation method according to any one of claims 3 to 7 in adsorbing lithium ions in a lithium-containing solution; wherein, The non-lithium alkali metal ions M1 in the lithium ion sieve adsorbent material spontaneously exchange ions with the lithium ions in the lithium-containing solution.

9. Application of the lithium ion sieve adsorbent material according to claim 1 or 2 or the lithium ion sieve adsorbent material prepared by the preparation method according to any one of claims 3 to 7 in the field of energy storage.

10. The use according to claim 9, characterized in that: The lithium ion sieve adsorbent material is used as a raw material for synthesizing anode materials of lithium ion batteries after adsorbing lithium ions.

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