Method and device for selectively extracting lithium from solution driven by photocatalytic reaction

Abstract

The invention provides a method and a device for selectively extracting lithium from a solution driven by a photocatalytic reaction, which are characterized in that a hydrogen evolution reaction of water is realized under the condition of illumination by using a reduction photocatalyst, and an oxidation reaction of hydrogen is realized under the condition of illumination by using an oxidation photocatalyst; the ion concentration difference between the hydrogen evolution reaction of water and the oxidation reaction of hydrogen is used as the dialysis driving force to drive lithium ions in the lithium-containing solution to selectively penetrate through the lithium ion selective membrane to enter the receiving liquid. The device comprises a gas oxidation chamber, a brine chamber, a lithium ion selective membrane, a liquid receiving chamber and a gas reduction chamber which are sequentially connected, an oxidation photocatalyst is arranged between the gas oxidation chamber and the brine chamber, a reduction photocatalyst is arranged between the liquid receiving chamber and the gas reduction chamber, and the gas oxidation chamber and the gas reduction chamber are connected through a gas channel. The method has the advantages of environmental friendliness, low comprehensive energy consumption, high ion selectivity and the like. The method is suitable for various lithium-containing brine, and is especially suitable for extracting lithium from western salt lakes and oceans with sufficient illumination.

Description

Technical Field

[0001] The present invention relates to lithium extraction technology, in particular to a method and device for continuous lithium extraction from a solution by dialysis driven by HER / HOR photocatalytic reaction, which is suitable for green lithium extraction from natural lithium-containing solutions such as salt lake brine or seawater. Background Art

[0002] With the rapid development of renewable energy and lithium battery industries, the demand for lithium resources has increased dramatically. Traditional lithium extraction methods, such as chemical precipitation, solvent extraction, adsorption, etc., each have some of the problems of high energy consumption, high cost, complex operation and environmental impact. New lithium extraction technologies, such as electrochemical methods, have the advantages of being environmentally friendly, low energy consumption and high selectivity. However, areas where natural lithium-containing solutions such as salt lakes and geothermal waters are distributed are often economically backward, with poor transportation and underdeveloped economies, and lack sufficient electricity to support the operation of large-scale electrochemical lithium extraction devices. Therefore, it is of great significance to develop a lithium extraction technology that does not rely on electricity while retaining the original advantages of electrochemical methods. Summary of the invention

[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a photocatalytic driven dialysis continuous lithium extraction method, which uses a photocatalyst to realize the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) of water under light conditions, and drives lithium ions to selectively permeate the lithium ion selective membrane, so as to separate and extract lithium from brine efficiently, at low cost and in an environmentally friendly manner.

[0004] The first aspect of the present invention provides a method for selective lithium extraction from a solution driven by a photocatalytic reaction, which utilizes a reducing photocatalyst to realize a hydrogen evolution reaction of water under light conditions, and utilizes an oxidizing photocatalyst to realize a hydrogen oxidation reaction under light conditions, and utilizes the ion concentration difference generated by the hydrogen evolution reaction and the hydrogen oxidation reaction in two chambers respectively as the driving force for dialysis, driving the lithium ions in the lithium-containing brine to selectively pass through the lithium ion selective membrane into the receiving solution, thereby realizing selective lithium extraction and enrichment of the brine.

[0005] The process is carried out under the condition of continuous flow of lithium-containing brine and receiving solution, and the lithium extraction efficiency and selectivity are controlled by adjusting the light intensity, the type and amount of HER and HOR catalysts, the flow rate of the lithium-containing solution and the receiving solution, the temperature of the reactor, and the material and parameters of the lithium ion selective membrane.

[0006] Furthermore, the oxidation photocatalyst is a metal, a metal oxide, a composite metal material or a metal organic framework. Preferably, the metal is one or more of Pt, Ru, NiO, and Ni; the metal oxide is one or more of RuO2, NiO, Ga2O3, and WO3; the composite metal material is one or more of Ru / VOC, Pt-C3N4, CdS, Ag@AgCl, PCN / rGO / PDIP, and Pt-C3N4 / Ag@AgCl; the metal organic framework is one or more of Ni-MOF-74-CdS / Co3O4 and Ru / MOFs.

[0007] Furthermore, the reduction photocatalyst is: a metal, a metal oxide, a sulfide, an alloy catalyst or a metal-organic framework. Preferably, the metal is one or more of Pt, Ru, NiO, and Ni; the metal oxide is one or more of TiO2, WO3, Ga2O3, and CuO; the sulfide is CdS, ZnS, ZnxCd 1-x S, one or more of MoS2; the metal-organic framework is one or more of MOF-199 / Ni, Ni-MOF-74-CdS / Co3O4.

[0008] Furthermore, the lithium ion selective membrane is a screening membrane that only allows lithium ions to pass through, and the lithium ion selective membrane is a ceramic membrane (CM), a polyethylene (propylene) microporous membrane (PMM), a composite membrane (LM), or a metal-organic framework membrane (MOF). The lithium ion selective membrane is based on the principle of dialysis separation, and the ion concentration difference induces the lithium ions to move through the ion exchange membrane, thereby achieving the purpose of ion separation.

[0009] Furthermore, the preparation method of the ceramic membrane is: Li2CO3, Al2O3, GeO2 and NH4H2PO4 are weighed respectively in a mass fraction of 1.5:0.5:1.5:3 and dissolved in an isopropanol solution, and the mixture is calcined at 600-800°C for 6-8h to obtain a ceramic membrane.

[0010] Furthermore, the lithium-containing solution is salt lake brine or battery recovery waste liquid or lithium-rich adsorbent solution or lithium-containing seawater; the receiving liquid is LiOH solution or dilute hydrochloric acid or lithium chloride or lithium sulfate.

[0011] The second aspect of the present invention is to provide a device for selective lithium extraction from a solution driven by a photocatalytic reaction, comprising: a gas oxidation chamber, a brine chamber, a lithium ion selective membrane, a receiving liquid chamber and a gas reduction chamber connected in sequence, an oxidation photocatalyst is arranged between the gas oxidation chamber and the brine chamber, and a reduction photocatalyst is arranged between the receiving liquid chamber and the gas reduction chamber.

[0012] Furthermore, both the brine chamber and the receiving liquid chamber are provided with liquid inlets and outlets, and lithium-containing brine and lithium hydroxide solution are pumped into the brine chamber at different flow rates through peristaltic pumps, respectively.

[0013] Furthermore, the oxidation photocatalyst and the reduction photocatalyst are coated on carbon paper.

[0014] The brine chamber and the receiving liquid chamber of the device are powered by two peristaltic pumps respectively, so as to realize the circulation of the brine and the receiving liquid.

[0015] The present invention utilizes the ion gradient distribution of the brine side and the receiving solution side generated by the photocatalytic reaction to drive the dialysis continuous lithium extraction. In addition, the introduction of the lithium ion selective membrane ensures that only lithium ions can be transferred from the brine to the receiving solution through the membrane, resulting in high selectivity and Faraday efficiency of lithium extraction.

[0016] Specifically, the redox process involves two main chemical reactions:

[0017] HER reaction: In the HER photocatalytic module, water is reduced to generate hydrogen (H2) and hydroxide ions (OH - ). The equation for this reaction is as follows:

[0018] 2H2O+2e - →H2+2OH -

[0019] HOR reaction: In the HOR photocatalytic module, hydrogen (H2) produced from the HER photocatalytic module flows into and reacts with hydroxide ions (OH - ) reaction, producing water through the hydrogen oxidation reaction (HOR). The equation for this reaction is as follows:

[0020] 2H2+2OH - →2H2O+2e -

[0021] Driven by the concentration difference generated by these two reactions, lithium ions (Li + ) migrates from the lithium-containing brine (left chamber) through the lithium ion selective membrane to the receiving solution (right chamber), while other cations are blocked, thereby achieving lithium extraction. In this way, continuous lithium extraction can be achieved with high lithium selectivity.

[0022] Advantages and beneficial effects of the present invention:

[0023] The present invention is driven by abundant light energy in the salt lake distribution area, reducing power consumption and operating costs. The photocatalytic process is environmentally friendly, reduces the use of chemical reagents, and reduces the impact on the environment. Through the design of photocatalysts and ion-selective membranes and the optimization of reaction conditions, high-efficiency and high-selectivity lithium extraction can be achieved, and the lithium selectivity can be close to 1. The method is applicable to various lithium-containing brines and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the photocatalytic oxygen reduction driven dialysis continuous lithium extraction system provided in Example 1 of the present invention.

[0025] Figure 2 This is a design diagram of the photocatalytic oxygen reduction driven dialysis continuous lithium extraction device provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are 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 creative work are within the scope of protection of the present invention.

[0027] The present invention provides a selective lithium extraction device in solution driven by a photocatalytic reaction, comprising a gas oxidation chamber, an oxidation photocatalyst, a brine chamber, a lithium ion selective membrane, a reduction photocatalyst, a receiving liquid chamber, and a gas reduction chamber. The specific scheme is as follows:

[0028] The volume of the gas oxidation chamber and the gas reduction chamber is 0.3 cm -3 The volume of brine chamber is 0.72ml and the volume of receiving liquid chamber is 0.72ml. The redox illumination area is 1.44cm -2

[0029] When in use, they are spliced ​​in sequence, with the oxidation photocatalyst located between the oxidation gas chamber and the brine chamber on the left, the lithium ion selective membrane intercalated between the brine chamber and the receiving liquid chamber, and the reduction photocatalyst located between the receiving liquid chamber and the reduction gas chamber on the right.

[0030] The brine chamber and the receiving liquid chamber are both provided with liquid inlet and outlet, and the brine and lithium hydroxide solution are respectively pumped into the chamber at different flow rates by peristaltic pumps. The gas oxidation chamber and the gas reduction chamber are connected by a gas channel.

[0031] The reaction chambers are all made of polytetrafluoroethylene, and anti-corrosion sealing pads are used between chambers. The device is assembled before use, deionized water is passed into the device to test the air tightness of the device, and then argon gas is passed into the device to test the air tightness of the device again. After two tests, the lithium extraction reaction can be carried out.

[0032] After the equipment is assembled according to the above requirements, light is applied, and the lithium hydroxide solution in the receiving liquid chamber undergoes a reduction reaction, generating hydrogen that enters the brine chamber for an oxidation photoreaction to generate water. The ion concentration difference generated in this process provides power for the lithium ion selective membrane between the brine chamber and the receiving liquid chamber to separate lithium ions.

[0033] Light source parameters Light source type: commonly used xenon lamp, UV lamp, LED light source, etc. Xenon lamp: simulates sunlight, usually choose 300W to 500W. LED light source: can choose a specific wavelength (such as 420nm, 450nm) for visible light response. UV lamp: wavelength 254nm or 365nm for ultraviolet light response. Use an optical power meter to measure, usually set at 100-200mW / cm 2 (Simulated sunlight).

[0034] Temperature: It can be carried out at room temperature (20-30°C), or heated in a constant temperature water bath or on a hot plate. Increasing the temperature usually helps to increase the reaction rate, but too high a temperature may cause the catalyst to deactivate.

[0035] Apply light to the reactor, set the light and reaction time, record the ion concentration in the collected liquid at 1, 2, 3, 4, 5, 6, 7 h, etc. (the reaction time can be adjusted according to the specific amount of the reactants), and calculate the Faraday efficiency and lithium selectivity and other data.

[0036] Faradaic efficiency is calculated by the following formula:

[0037] FE=Z·V·ΔC Li + / Q

[0038] Z is the charge number of the lithium ion. For lithium ions, Z=1.

[0039] F is the Faraday constant, which is approximately 96485 C / mol (coulomb / mole).

[0040] V is the volume of feed solution flowing through the reactor.

[0041] ΔC Li + Changes in lithium ion concentration in the receiving solution.

[0042] Q charge consumption can be calculated by multiplying current and time, that is, Q = I·t, where I is the photocurrent and t is time.

[0043] In the process of photocatalytic lithium extraction, the lithium selectivity can be calculated by testing the lithium purity in the receiving solution using the following formula:

[0044] P Li (%) = C Li / C i *100

[0045] P Li Lithium ion purity

[0046] C Li Lithium ion concentration

[0047] C i All ion concentrations including Na + Mg 2+ , K +

[0048] The lithium extraction performance data of the device is obtained through calculation.

[0049] In order to make the technical solution of the present invention more clear, the following will be described in detail with examples, but the content of the present invention is not limited to the scope of the enumerated implementation modes.

[0050] Example 1

[0051] 1) Weigh 1 g of each of the oxidation photocatalyst RuO2 and the reduction photocatalyst TiO2, add them into 1 ml of ethanol solvent and disperse them ultrasonically at room temperature for 1 h. Take 50 μL and spread it evenly on the surface of carbon paper, and bake it under a baking lamp for 20 min.

[0052] 2) Li2CO3, Al2O3, GeO2 and NH4H2PO4 were weighed in a mass fraction of 1.5:0.5:1.5:3 and dissolved in an isopropanol solution, and the mixture was calcined at 600°C for 6 hours to prepare a lithium ion selective membrane.

[0053] 3) The reactor is designed to include a gas oxidation chamber, an oxidation photocatalyst, a brine chamber, a lithium ion selective membrane, a reduction photocatalyst, a receiving liquid chamber, and a gas reduction chamber. The specific scheme is as follows:

[0054] The oxidation photocatalyst is placed between the gas oxidation chamber and the brine chamber, the reduction photocatalyst is placed between the receiving liquid chamber and the gas reduction chamber, and the lithium ion selective membrane is placed between the brine chamber and the receiving liquid chamber.

[0055] 4) Prepare brine with a lithium concentration of 70ppm (0.01M) and a sodium concentration of 2,300ppm (0.1M) and pass it into the brine chamber, prepare lithium hydroxide (0.1M) solution and pass it into the receiving liquid chamber, with a flow rate of 3ml / min.

[0056] 5) The reactor was operated at room temperature (25°C), and the light was turned on for 10 hours. The receiving solution was collected every 1 hour and the lithium ion concentration was tested by ICP. After 10 hours of operation, the Faraday efficiency of the device was calculated to be 89%, and the lithium purity in the receiving solution was 95%.

[0057] Example 2

[0058] The difference between Example 2 and Example 1 is that step 2) uses a perovskite structure lithium ion selective membrane. Weigh 5g LiNO3 and 8g La(NO)3 and dissolve them in 20ml 25% citric acid aqueous solution, add titanium butoxide during stirring, and heat to 100°C to obtain a uniform solution. The solution is evaporated to dryness at 150°C, and the mixture is calcined, heated to 600°C at 2°C / min and sintered for 4h, and then sintered at 900°C for 20h to obtain a powder. The powder is placed in a ball mill and ball milled at 300rpm for 12h to obtain nanoparticles with a diameter of 200nm, which are loaded into a tungsten carbide (WC) mold and pressed into a disc blank with a diameter of 22mm and a thickness of 70μm. It is sintered at 1100°C in a high-temperature furnace for 8 hours to obtain a molten membrane, and the heating and cooling procedures are both 2°C / min. An ion selective membrane with a perovskite structure is obtained.

[0059] Prepare simulated brine with a lithium concentration of 150 ppm and a sodium concentration of 2000 ppm, and prepare lithium hydroxide (0.1 M) as a receiving solution.

[0060] The system is operated at a light intensity of 200mW / cm 2 The temperature is controlled at 30℃.

[0061] The flow rates of brine and receiving solution were set to 4 ml / min and 3 ml / min respectively. The prepared membrane was put into the device and operated for 20 hours. The faradaic efficiency of the device was finally calculated by testing to be 91%, and the purity of lithium in the receiving solution was 97%.

[0062] Example 3

[0063] The difference between Example 3 and Example 1 is only in step 4) testing the lithium extraction performance of the device in simulated brine of different concentrations. The specific operation is as follows: brine with a lithium concentration of 140ppm (0.05M) and a sodium concentration of 300ppm (0.1M) is introduced into the brine chamber, and a receiving solution of lithium hydroxide (0.1M) is introduced into the receiving solution chamber at a flow rate of 5ml / min. The device is operated for 20h and the faradaic efficiency of the device obtained by the test calculation is 94%, and the lithium purity in the receiving solution is 97%.

[0064] Example 4

[0065] The only difference between Example 4 and Example 1 is that in step 1), a Pt-C3N4 / Ag@AgCl composite catalyst is used as an oxidation photocatalyst and MoS2 is used as a reduction photocatalyst in the photocatalytic system to optimize the photocatalytic efficiency of HER (hydrogen evolution reaction) and HOR (hydrogen oxidation reaction).

[0066] Brine with a lithium concentration of 120 ppm and a sodium concentration of 1,800 ppm was used as the experimental medium, and the receiving solution was lithium hydroxide (0.1 M).

[0067] Use 450nm LED light source with light intensity of 100mW / cm 2 , the temperature is set to 25℃.

[0068] The flow rate was set at 5 ml / min and the illumination was continuous for 20 h.

[0069] The faradaic efficiency of the device finally obtained through testing and calculation is 91%, and the purity of lithium in the receiving solution is 96%.

[0070] Example 5

[0071] The difference between Example 5 and Example 1 is that in step 5), the reactor is illuminated and the light intensity of the LED light source is adjusted to 50 mW / cm 2 、100mW / cm 2 、150mW / cm 2 , flow rate is 4ml / min, light duration is 40h, receiving solution is collected every 1 hour and lithium ion concentration is tested by ICP, the prepared photocatalyst is put into the device and operated for 40h. Light intensity is 50mW / cm 2 : Lithium extraction efficiency is 75%. Light intensity 100mW / cm 2 : Lithium extraction efficiency is 92%. Light intensity is 150mW / cm 2 : The lithium extraction efficiency is 95%, but the energy consumption increases significantly. The optimal light intensity is 100mW / cm 2, a balance is achieved between efficiency and energy consumption. The faradaic efficiency of the device is calculated to be 92%, and the lithium purity in the receiving solution is 95%.

[0072] Example 6

[0073] The difference between Example 6 and Example 1 is that in step 4), salt lake brine (Li+ concentration is 100 ppm, Na+ concentration is 500 ppm, and Mg2+ concentration is 500 ppm) is taken. The pH value of the brine is adjusted to 7.5 to prevent metal ion precipitation. In the redox dialysis device, the brine is injected into the brine chamber, and the LED light source (light intensity 120 mW / cm 2 ).

[0074] After 4 hours of treatment, the concentration of Li+ enriched solution increased to 800ppm. The faradaic efficiency was 93%, the lithium purity in the receiving solution was 96%, and Mg2+ almost did not pass through the membrane.

[0075] Example 7

[0076] The difference between Example 7 and Example 1 is that in step 4), brine with a lithium concentration of 70ppm (0.01M) and a sodium concentration of 2,300ppm (0.1M) is introduced into the brine chamber, and a receiving solution of lithium hydroxide (0.1M) is introduced into the receiving solution chamber at a flow rate of 3ml / min. Dialysis experiments were carried out for 3 hours under different pH conditions. pH=5: The Faraday efficiency of lithium extraction is 80%. pH=7: The Faraday efficiency of lithium extraction is 92%. pH=9: The Faraday efficiency of lithium extraction is 85%. Selecting pH=7 as the optimal condition can ensure high Faraday efficiency and high lithium selectivity.

[0077] Example 8

[0078] The difference between Example 8 and Example 1 is that the reaction temperature is changed in step 5), and the reaction temperature is set to 20, 30, 40, and 50°C, respectively, to test the lithium extraction efficiency of the device at different temperatures. Brine with a lithium concentration of 70ppm (0.01M) and a sodium concentration of 2300ppm (0.1M) is introduced into the brine chamber, and a receiving solution with lithium hydroxide (0.1M) is introduced into the receiving solution chamber, with a flow rate of 3ml / min, and the reaction is performed for 10 hours respectively.

[0079] Through experiments, it was found that at a temperature of 20°C, a Faraday efficiency of 90% and a lithium purity of 95% can be achieved, and at a temperature of 30°C, a Faraday efficiency of 98% and a lithium purity of 97% can be achieved. At a temperature of 40°C, a Faraday efficiency of 95% and a lithium purity of 94% can be achieved, and at a temperature of 50°C, a Faraday efficiency of 95% and a lithium purity of 93% can be achieved. Therefore, the reaction temperature of 30°C is selected to ensure high Faraday efficiency and high lithium selectivity.

[0080] Comparative Example 1

[0081] The lithium extraction method provided in this comparative example is basically the same as that in Example 1, except that the photocatalytic module in the device is not used: the photocatalytic module in the device is replaced with a conductor electrode, and a voltage is applied at both ends. Experimental conditions: electrode voltage: 2V; current density: 10mA / cm 2 Experimental time: 10 hours. Prepare brine with lithium concentration of 100 ppm and sodium concentration of 2000 ppm, and the receiving liquid is lithium hydroxide (0.1 M), and perform dialysis for 10 hours at room temperature.

[0082] Comparative Example 2

[0083] The lithium extraction method provided in this comparative example is basically the same as that in Example 1, except that the lithium ion selective membrane is replaced by a common cation exchange membrane:

[0084] The lithium ion selective membrane in the device was replaced with a common cation exchange membrane, and other conditions remained unchanged. The lithium extraction experiment was still carried out for 10 hours.

[0085] Comparative Example 3

[0086] The lithium extraction method provided in this comparative example is basically the same as that in Example 1, except that the photocatalytic module is not used and the lithium ion selective membrane is replaced by a common cation exchange membrane:

[0087] The photocatalyst in the device was removed, the lithium ion selective membrane was replaced with a common cation exchange membrane, and other conditions remained unchanged. The lithium extraction experiment was still carried out for 10 hours.

[0088]

[0089]

[0090] It can be seen from Table 1 that by using the photocatalytic HER / HOR photodialysis device provided in Examples 1-8 of the present invention for photochemical lithium extraction, under different photocatalytic materials, different lithium ion selective membranes, different solution concentrations and other conditions, 90% Faraday efficiency and lithium ion selectivity close to the theoretical value can be achieved. In Comparative Example 1, the use of electrodialysis to apply an external voltage to the reactor results in a relatively high energy consumption for the entire system. Photocatalytic oxygen uses solar energy for redox reaction to drive dialysis, which greatly reduces the overall energy consumption. Comparative Example 2 cannot ensure ion selectivity due to the lack of a lithium ion efficient selective membrane. Comparative Example 3 cannot achieve the separation of lithium ions and other ions. It is fully demonstrated that the heterostructure core-shell nickel cobalt manganese oxide material provided by the present invention has a high lithium extraction efficiency.

[0091] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for selectively extracting lithium from a solution driven by a photocatalytic reaction, characterized in that: A reducing photocatalyst is used to realize the hydrogen evolution reaction of water under light conditions, and an oxidizing photocatalyst is used to realize the hydrogen oxidation reaction under light conditions. The ion concentration difference generated by the hydrogen evolution reaction of water and the hydrogen oxidation reaction in the two chambers is used as the driving force of dialysis, driving the lithium ions in the lithium-containing solution to selectively pass through the lithium ion selective membrane into the receiving solution, thereby realizing the selective extraction and enrichment of lithium from brine.

2. The method for selectively extracting lithium from a solution driven by a photocatalytic reaction according to claim 1, characterized in that: The process is carried out under the condition of continuous flow of the lithium-containing solution and the receiving solution, and the lithium extraction efficiency and selectivity are controlled by adjusting the light intensity, the type and amount of HER and HOR catalysts, the flow rates of the lithium-containing solution and the receiving solution, the temperature of the reactor, and the material and parameters of the lithium ion selective membrane.

3. The method for selectively extracting lithium from a solution driven by a photocatalytic reaction according to claim 1, characterized in that: The oxidative photocatalyst is a metal, a metal oxide, a composite metal material or a metal organic framework, wherein the metal is one or more of Pt, Ru, NiO and Ni; the metal oxide is one or more of RuO2, NiO, Ga2O3 and WO3; the composite metal material is one or more of Ru / VOC, Pt-C3N4, CdS, Ag@AgCl, PCN / rGO / PDIP and Pt-C3N4 / Ag@AgCl; the metal organic framework is one or more of Ni-MOF-74-CdS / Co3O4 and Ru / MOFs.

4. The method for selectively extracting lithium from a solution driven by a photocatalytic reaction according to claim 1, characterized in that: The reducing photocatalyst is: a metal, a metal oxide, a sulfide, an alloy catalyst or a metal-organic framework, wherein the metal is one or more of Pt, Ru, NiO, and Ni; the metal oxide is one or more of TiO2, WO3, Ga2O3, and CuO; the sulfide is one or more of CdS, ZnS, ZnxCd1-xS, and MoS2; and the metal-organic framework is one or more of MOF-199 / Ni and Ni-MOF-74-CdS / Co3O4.

5. The method for selective lithium extraction from solution driven by photocatalytic reaction according to claim 1, characterized in that: The lithium ion selective membrane is a ceramic membrane, a polyethylene microporous membrane, a polypropylene microporous membrane or a composite membrane, or a metal-organic framework membrane.

6. The method for selectively extracting lithium from a solution driven by a photocatalytic reaction according to claim 5, characterized in that: The ceramic membrane preparation method is as follows: Li2CO3, Al2O3, GeO2 and NH4H2PO4 are weighed respectively in a mass fraction of 1.5:0.5:1.5:3 and dissolved in an isopropanol solution, and the mixture is calcined at 600-800°C for 6-8h to obtain a ceramic membrane.

7. The method for selectively extracting lithium from a solution driven by a photocatalytic reaction according to claim 1, characterized in that: The lithium-containing solution is salt lake brine or battery recovery waste liquid or lithium-rich adsorbent solution or lithium-containing seawater; the receiving liquid is LiOH solution or dilute hydrochloric acid or lithium chloride or lithium sulfate.

8. A device for selectively extracting lithium from a solution driven by a photocatalytic reaction according to any one of claims 1 to 7, characterized in that: include: The gas oxidation chamber, brine chamber, lithium ion selective membrane, receiving liquid chamber and gas reduction chamber are connected in sequence, an oxidation photocatalyst is arranged between the gas oxidation chamber and the brine chamber, a reduction photocatalyst is arranged between the receiving liquid chamber and the gas reduction chamber, and the gas oxidation chamber and the gas reduction chamber are connected through a gas channel.

9. The device according to claim 8, characterized in that The brine chamber and the receiving liquid chamber are both provided with liquid inlets and outlets, and brine and lithium hydroxide solution are respectively pumped into the chamber at different flow rates through peristaltic pumps.

10. The device according to claim 8, characterized in that The oxidation photocatalyst and the reduction photocatalyst are coated on carbon paper.

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