WO2024259615A1 - 一种制备电解质盐的方法 - Google Patents

一种制备电解质盐的方法 Download PDF

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WO2024259615A1
WO2024259615A1 PCT/CN2023/101596 CN2023101596W WO2024259615A1 WO 2024259615 A1 WO2024259615 A1 WO 2024259615A1 CN 2023101596 W CN2023101596 W CN 2023101596W WO 2024259615 A1 WO2024259615 A1 WO 2024259615A1
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lithium
electrode
preparing
hexafluorophosphate
electrolyte salt
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French (fr)
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李爱霞
谢英豪
余海军
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/101596 priority patent/WO2024259615A1/zh
Priority to ARP240101297A priority patent/AR132757A1/es
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present invention relates to the technical field of lithium extraction from salt lakes, and in particular to a method for preparing electrolyte salts.
  • Lithium and its compounds are important raw materials used in metallurgy, nuclear reactions and chemical industries. In particular, with the rapid development of the lithium battery industry in recent years, our demand for lithium has surged.
  • Electrolyte is one of the four main materials of lithium-ion batteries.
  • the main components of lithium battery electrolyte are solvents, solutes and additives.
  • the solute is a provider of lithium ions.
  • lithium hexafluorophosphate is the most widely used. At present, lithium hexafluorophosphate is mainly prepared by dissolving lithium halide in anhydrous hydrogen fluoride and then introducing high-purity PF 5 gas for reaction.
  • Salt lake brine contains huge lithium resources, so lithium extraction from salt lakes is gaining more and more attention.
  • the main methods for extracting lithium from salt lake brine include precipitation, adsorption, carbonization, calcination leaching and solvent extraction.
  • Solvent extraction is widely used.
  • FeCl 3 is inevitably used as a co-extractant, which increases the density of the extracted organic phase and reduces the density difference between the two phases.
  • the extraction and separation equipment has high requirements. Traditional mixing and settling tanks are difficult to meet the process requirements. High-efficiency centrifugal extraction equipment must be used, and the equipment cost is expensive.
  • the organic phase contains the co-extractant FeCl 3 , the brine must be kept weakly acidic, otherwise it will cause Fe hydrolysis, and the brine entering the extraction section must be acidified.
  • salt lake brine usually contains cations such as Na + and K + .
  • concentration of coexisting cations When the concentration of coexisting cations is too high, they are easy to enter the extract together with Li + , causing adverse effects on the extraction and separation of Li + .
  • salt lake brine with a high sodium-lithium ratio when extracting lithium, it is necessary to pre-treat the salt lake brine with a high sodium-lithium ratio to reduce the mass ratio of Na + to Li + , or further remove Na+, K +, etc. after stripping, resulting in a long production cycle.
  • This article is to overcome the shortcomings of the prior art and provide a method for preparing an electrolyte salt, which can prepare LiPF6 electrolyte salt.
  • a method for preparing an electrolyte salt comprises the following steps:
  • Extracting salt lake brine with an organic phase to obtain a lithium-rich organic phase, wherein the organic phase includes an extractant and a hexafluorophosphate ionic liquid;
  • An electrolysis device including an anode chamber and a cathode chamber is provided, wherein a lithium-rich electrode is used as an anode, a lithium-poor electrode is used as a cathode, a lithium hexafluorophosphate solution is used as an anode electrolyte, and a lithium-rich organic phase is used as a cathode electrolyte for electrolysis;
  • the positions of the lithium-rich electrode and the lithium-poor electrode are interchanged, and electrolysis is performed to form lithium hexafluorophosphate electrolyte salt in the anode chamber.
  • the salt lake brine is first extracted with an organic phase to obtain a lithium-rich organic phase, and the lithium-rich organic phase is used as the cathode electrolyte for electrolysis, which can enrich lithium and recover it to the anode chamber while generating lithium hexafluorophosphate.
  • the lithium-rich electrodes and lithium-poor electrodes for electrolysis, it has a high selectivity for lithium, which can effectively prevent other impurity ions from being extracted into the organic phase and prevent impurity ions from entering the anode chamber.
  • the lithium ions of the lithium-rich organic phase are embedded in the lithium-poor electrode, and the lithium ions of the lithium-rich electrode are released into the anode electrolyte.
  • the lithium ions embedded in the lithium-poor electrode are released, and the [PF 6 ] - in the ionic liquid of the cathode chamber enters the organic solution of the anode chamber through the membrane to form LiPF 6 electrolyte salt.
  • the electrolysis device is a conventional electrolysis device in the art, such as an electrolytic cell.
  • the volume ratio of the organic phase to the salt lake brine is (0.5-4):1; controlling the volume ratio of the organic phase to the salt lake brine within this range can effectively enrich the lithium in the salt lake brine.
  • the volume ratio of the organic phase to the salt lake brine is (1-2): 1. Controlling the volume ratio of the organic phase to the salt lake brine within this range can effectively enrich the lithium in the salt lake brine, and at the same time, the phase separation speed and extraction speed are good.
  • the volume ratio of the extractant to the hexafluorophosphate ionic liquid is (5-30):(60-95).
  • the volume ratio of the extractant to the hexafluorophosphate ionic liquid is (10-30): (60-95).
  • the volume ratio of the extractant to the hexafluorophosphate ionic liquid is (10-20): (80-90).
  • the extractant is tributyl phosphate.
  • the hexafluorophosphate ionic liquid is at least one of 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, and 1-octyl-3-methylimidazolium hexafluorophosphate.
  • tributyl phosphate is used as the extractant, which has high selectivity and high extraction rate for lithium and will not emulsify.
  • Phenomenon avoid the use of ferric chloride co-extraction agent, do not need to acidify the brine, this paper directly electrolyzes after extraction, avoids the subsequent stripping process using a large amount of high-concentration acidic liquid to damage the equipment, and simplifies the extraction process.
  • the hexafluorophosphate ionic liquid has stable properties and can provide [PF 6 ] - to the system, which can then react with lithium ions released from the lithium-poor electrode to form LiPF 6 electrolyte salt in the ionic liquid of the cathode chamber.
  • the membrane comprises an anion exchange membrane.
  • the lithium-rich electrode is at least one of a LiMn 2 O 4 electrode, a LiFePO 4 electrode, a Li 2 TiO 3 electrode, a Li 7 Ti 5 O 12 electrode, and a LiNi x Co y Mn 1-xy O 2 electrode;
  • the representative LiNi x Co y Mn 1-xy O 2 electrode is LiNi 1/3 Co 1/3 Mn 1/3 O 2 (abbreviated as NCM333) electrode.
  • LiFePO 4 electrode as an example: LiFePO 4 , a conductive agent, and a binder are uniformly mixed in a mass ratio of (70-85): (8-15): (8-15), applied on the surface of the current collector, and dried to obtain the LiFePO 4 electrode.
  • the coating amount is 10 to 30 mg/cm 2 .
  • the conductive agent is at least one of carbon black, acetylene black, carbon nanotubes, and graphene.
  • the binder is PVDF.
  • LiMn 2 O 4 electrode When it is a LiMn 2 O 4 electrode, a Li 2 TiO 3 electrode, a Li 7 Ti 5 O 12 electrode, or a LiNi x Co y Mn 1-xy O 2 electrode, it is only necessary to replace LiFePO 4 with the corresponding LiMn 2 O 4 , Li 2 TiO 3 , Li 7 Ti 5 O 12 , or LiNi x Co y Mn 1-xy O 2 .
  • the lithium-poor electrode is at least one of a Li 1-a MnO 4 electrode, a Li 1-a FePO 4 electrode, a Li 2-b TiO 3 electrode, a Li 7-c Ti 5 O 12 electrode, and a Li 1-a Ni x Co y Mn 1-xy O 2 electrode;
  • the preparation method of the lithium-poor electrode is illustrated by taking the Li 1-a FePO 4 electrode as an example: the LiFePO 4 electrode prepared as above is used as the positive electrode, and the AgCl electrode is used as the negative electrode, which are placed in an electrolyte and delithiation is performed at a constant voltage.
  • the current is as low as 0.2 mA, the reaction is stopped to obtain a Li 1-a FePO 4 electrode.
  • This article first uses a lithium-rich electrode as the anode and a lithium-poor electrode as the cathode.
  • the lithium ions in the lithium-rich organic phase are embedded in the lithium-poor electrode, and the lithium ions in the lithium-rich electrode are released into the anode electrolyte.
  • the lithium ions embedded in the lithium-poor electrode are released, and the [PF 6 ] - in the ionic liquid in the cathode chamber passes through the membrane into the organic solution in the anode chamber to form LiPF 6 electrolyte salt.
  • the lithium hexafluorophosphate solution includes lithium hexafluorophosphate and an organic solvent.
  • the concentration of lithium hexafluorophosphate in the lithium hexafluorophosphate solution is 20-100 mmol/L.
  • the concentration of lithium hexafluorophosphate in the lithium hexafluorophosphate solution is 40-60 mmol/L.
  • the organic solvent is at least one of dimethyl carbonate, propylene carbonate, ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate.
  • dimethyl carbonate, propylene carbonate, ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate as organic solvents, after electrolysis, the solution in the anode chamber is a mixed solution of high-purity lithium hexafluorophosphate and the organic solvent, and the solution in the anode chamber can be directly used as the electrolyte of the secondary battery.
  • the voltage of the electrolysis is 1-4V.
  • This paper first extracts salt lake brine with an organic phase to obtain a lithium-rich organic phase, and uses the lithium-rich organic phase as the cathode electrolyte for electrolysis, which can enrich lithium and recover it to the anode chamber while generating lithium hexafluorophosphate.
  • lithium-rich electrodes and lithium-poor electrodes for electrolysis, it has a high selectivity for lithium, which can effectively prevent other impurity ions from being extracted into the organic phase and prevent impurity ions from entering the anode chamber.
  • the lithium ions in the lithium-rich organic phase are embedded in the lithium-poor electrode, and the lithium ions in the lithium-rich electrode are released into the anode electrolyte.
  • a method for preparing an electrolyte salt comprises the following steps:
  • LiFePO 4 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, and coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 and dried to obtain LiFePO 4 lithium-rich electrode. State electrode.
  • lithium-poor electrode The lithium-rich LiFePO4 electrode prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode. The electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 1.1 V. The reaction is stopped when the current drops to 0.2 mA to obtain a lithium-poor Li1 - aFePO4 electrode.
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • the LiFePO4 lithium-rich electrode and the Li1 -aFePO4 lithium -poor electrode are taken out and rinsed, and then the positions of the two are swapped (i.e., the LiFePO4 lithium-rich electrode is placed in the cathode chamber, and the Li1 - aFePO4 lithium- poor electrode is placed in the anode chamber).
  • a voltage of 2 V is applied to the cathode and cathode, and electrolysis is performed at room temperature for 1.5 h.
  • the solution in the anode chamber is the LiPF6 electrolyte salt.
  • a method for preparing an electrolyte salt comprises the following steps:
  • LiMn 2 O 4 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 , and dried to obtain a LiMn 2 O 4 lithium-rich electrode.
  • Step (2) Preparation of lithium-poor electrode:
  • the lithium -rich LiMn2O4 electrode prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode.
  • the electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 1.1 V. The reaction is stopped when the current drops to 0.2 mA to obtain a Li1 - aMn2O4 lithium -poor electrode.
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • the electrolytic cell is divided into an anode chamber and a cathode chamber by an anion exchange membrane, a LiMn2O4 lithium -rich electrode is placed in the anode chamber as an anode, and a Li1 - aMn2O4 lithium -poor electrode is placed in the cathode chamber as a cathode, a lithium hexafluorophosphate solution is used as an anolyte, and a lithium-rich organic phase is used as a cathode electrolyte, a voltage of 2.3 V is applied to the anode and cathode, and electrolysis is performed at room temperature for 1 hour;
  • the LiMn2O4 lithium -rich electrode and the Li1 - aMn2O4 lithium -poor electrode are taken out and rinsed, and then their positions are swapped (i.e., the LiMn2O4 lithium -rich electrode is placed in the cathode chamber, and the Li1 -aMn2O4 lithium - poor electrode is placed in the anode chamber).
  • a voltage of 2.3V is applied to the cathode and cathode, and electrolysis is carried out at room temperature for 1 hour.
  • the solution in the anode chamber is LiPF6 electrolyte salt.
  • a method for preparing an electrolyte salt comprises the following steps:
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 , and dried to obtain LiNi 1/3 Co 1/3 Mn 1/3 O 2 lithium-rich electrode.
  • lithium-poor electrode The lithium-rich electrode LiNi1 /3Co1 / 3Mn1 / 3O2 prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode. The electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 1.1 V. The reaction is stopped when the current drops to 0.2 mA to obtain a lithium-poor electrode LiNi1 -dCo1 / 3Mn1 /3O2 .
  • tributyl phosphate and 1-hexyl-3-methylimidazolium hexafluorophosphate were mixed in a volume ratio of 80:20 to obtain an organic phase, and salt lake brine was used as an aqueous phase.
  • the organic phase and the aqueous phase were placed on a constant temperature oscillator in a volume ratio of 2:1 for 30 minutes to mix evenly, allowed to stand for 20 minutes, and centrifuged to obtain a lithium-rich organic phase;
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • a method for preparing an electrolyte salt comprises the following steps:
  • LiFePO 4 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 , and dried to obtain a LiFePO 4 lithium-rich electrode.
  • lithium-poor electrode The lithium-rich LiFePO4 electrode prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode. The electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 1.1 V. The reaction is stopped when the current drops to 0.2 mA to obtain a lithium-poor Li1 - aFePO4 electrode.
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 0.55g/L, Na + 49.39g/L, Mg 2+ 122.42g/L, K + 16.97g/L, B 5.37g/L, Cl - 72.19g/L.
  • the electrolytic cell is divided into an anode chamber and a cathode chamber by an anion exchange membrane, a LiFePO4 lithium-rich electrode is placed in the anode chamber as an anode, and a Li1 - aFePO4 lithium-poor electrode is placed in the cathode chamber as a cathode, a lithium hexafluorophosphate solution is used as an anolyte, and a lithium-rich organic phase is used as a cathode electrolyte, and a positive electrode is applied to the positive and negative electrodes. Apply 2V voltage and electrolyze for 1.5h at room temperature;
  • the LiFePO4 lithium-rich electrode and the Li1 -aFePO4 lithium -poor electrode are taken out and rinsed, and then the positions of the two are swapped (i.e., the LiFePO4 lithium-rich electrode is placed in the cathode chamber, and the Li1 - aFePO4 lithium- poor electrode is placed in the anode chamber).
  • a voltage of 2 V is applied to the cathode and cathode, and electrolysis is performed at room temperature for 1.5 h.
  • the solution in the anode chamber is the LiPF6 electrolyte salt.
  • a method for preparing an electrolyte salt comprises the following steps:
  • Li 2 TiO 3 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 , and dried to obtain a Li 2 TiO 3 lithium-rich electrode.
  • lithium-poor electrode The lithium-rich Li2TiO3 electrode prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode. The electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 1.1 V. The reaction is stopped when the current drops to 0.2 mA to obtain a lithium-poor Li2 -bTiO3 electrode .
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • the electrolytic cell is divided into an anode chamber and a cathode chamber by an anion exchange membrane, a Li2TiO3 lithium -rich electrode is placed in the anode chamber as an anode, and a Li2 -bTiO3 lithium -poor electrode is placed in the cathode chamber as a cathode, a lithium hexafluorophosphate solution is used as an anolyte, and a lithium-rich organic phase is used as a cathode electrolyte, a voltage of 2 V is applied to the anode and cathode, and electrolysis is carried out at room temperature for 1.5 h;
  • the Li2TiO3 lithium -rich electrode and the Li2 -b TiO3 lithium -poor electrode are taken out and rinsed, and then their positions are swapped (i.e., the Li2TiO3 lithium -rich electrode is placed in the cathode chamber, and the Li2 -b TiO3 lithium- poor electrode is placed in the anode chamber).
  • a voltage of 2V is applied to the cathode and cathode, and electrolysis is carried out at room temperature for 1.5h.
  • the solution in the anode chamber is LiPF6 electrolyte salt.
  • a method for preparing an electrolyte salt comprises the following steps:
  • LiFePO 4 , carbon black and PVDF were mixed evenly in a mass ratio of 80:10:10, coated on the surface of carbon cloth at a coating amount of 15 mg/cm 2 , and dried to obtain a LiFePO 4 lithium-rich electrode.
  • lithium-poor electrode The lithium-rich LiFePO4 electrode prepared in step (1) is used as the positive electrode and the AgCl electrode is used as the negative electrode. The electrodes are placed in a 0.5 mol/L NaCl electrolyte and delithiation is performed at a voltage of 2 V. The reaction is stopped when the current drops to 0.2 mA to obtain a lithium-poor Li1 - aFePO4 electrode.
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • the electrolytic cell is divided into an anode chamber and a cathode chamber by an anion exchange membrane.
  • a LiFePO4 lithium-rich electrode is placed in the anode chamber as an anode, and a Li1 - aFePO4 lithium-poor electrode is placed in the cathode chamber as a cathode.
  • a lithium hexafluorophosphate solution is used as the anode electrolyte, and a lithium-rich organic phase is used as the cathode electrolyte.
  • a voltage of 2 V is applied to the cathode and cathode. Electrolysis is carried out at room temperature for 1.5 h.
  • the solution in the anode chamber is the LiPF6 electrolyte salt.
  • Comparative Example 2 was back-extracted with hydrochloric acid after extraction.
  • a method for preparing an electrolyte salt comprises the following steps:
  • tributyl phosphate and 1-butyl-3-methylimidazolium hexafluorophosphate were mixed in a volume ratio of 85:15 to obtain an organic phase, and salt lake brine was used as an aqueous phase.
  • the organic phase and the aqueous phase were placed on a constant temperature oscillator in a volume ratio of 1.5:1 for 30 minutes to mix, and then allowed to stand for 20 minutes, and centrifuged to obtain a lithium-rich organic phase;
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 1.59g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.
  • Comparative Example 3 was back-extracted with hydrochloric acid after extraction.
  • a method for preparing an electrolyte salt comprises the following steps:
  • tributyl phosphate and 1-butyl-3-methylimidazolium hexafluorophosphate were mixed in a volume ratio of 85:15 to obtain an organic phase, and salt lake brine was used as an aqueous phase.
  • the organic phase and the aqueous phase were placed on a constant temperature oscillator in a volume ratio of 1.5:1 for 30 minutes to mix, and then allowed to stand for 20 minutes, and centrifuged to obtain a lithium-rich organic phase;
  • the ion concentrations (g/L) contained in the salt lake brine are: Li + 0.55g/L, Na + 98.56g/L, Mg 2+ 92.47g/L, K + 20.33g/L, B 6.03g/L, Cl - 273.1g/L.

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Abstract

本文公开了一种制备电解质盐的方法，属于盐湖提锂技术领域，本文先将盐湖卤水用有机相进行萃取，得到富锂有机相，以富锂有机相作为阴极电解液进行电解，能够使锂富集回收到阳极室的同时生成六氟磷酸锂，采用富锂态电极和贫锂态电极电解时，对锂具有较高的选择性，可以有效的避免其他杂质离子被萃取到有机相中，阴极室离子液体中的[PF6]-通过膜进入阳极室的有机溶液中形成LiPF6电解质盐。

Description

一种制备电解质盐的方法 技术领域
本文涉及盐湖提锂技术领域，具体涉及一种制备电解质盐的方法。
背景技术
锂及其化合物是冶金、核反应和化学工业中使用的重要原材料，特别是近年来随着锂电池行业的快速发展，使我们对锂的需求量激增，电解液是锂离子电池四大主材之一，锂电池电解液的主要成分是溶剂、溶质和添加剂，溶质作为锂离子的提供者，其中应用最为广泛的为六氟磷酸锂，目前主要是将卤化锂溶解在无水氟化氢中，再通入高纯PF5气体进行反应制备六氟磷酸锂。
盐湖卤水赋存储量巨大的锂资源，因此盐湖提锂越来越受到人们的重视，现阶段，盐湖卤水中提锂的方法主要有沉淀法、吸附法、碳化法、煅烧浸取法和溶剂萃取法等，其中溶剂萃取法应用较为广泛，使用溶剂萃取法都不可避免地采用了FeCl3作为协萃剂，使得萃取有机相密度增大，两相密度差减小，对萃取分离设备要求较高，传统的混合澄清槽难以满足工艺要求，要采用高效的离心萃取设备，设备造价昂贵；此外，由于有机相中含有协萃剂FeCl3，这就要求卤水必须保持弱酸性，否则就会造成Fe水解，进入萃取工段的卤水必须进行酸化处理。
另外，盐湖卤水中通常含有Na+、K+等阳离子，当共存的阳离子浓度过高时，容易和Li+一起进入到萃取液中，给Li+的萃取分离造成不良影响。对于高钠锂比的盐湖卤水，进行萃取提取锂时，需要对高钠锂比的盐湖卤水进行预处理以降低Na+与Li+的质量比，或在反萃后进行进一步除Na+、K+等，导致生产周期过长。
发明内容
本文的目的在于克服现有技术存在的不足之处而提供一种制备电解质盐的方法，能够制备得到LiPF6电解质盐。
为实现上述目的，本文采取的技术方案为：
一种制备电解质盐的方法，包括以下步骤：
用有机相萃取盐湖卤水，得到富锂有机相，所述有机相包括萃取剂和六氟磷酸盐离子液体；
提供包括阳极室和阴极室的电解装置，以富锂态电极为阳极，以贫锂态电极为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，进行电解；
将富锂态电极和贫锂态电极位置互换，再进行电解，在阳极室形成六氟磷酸锂电解质盐。
本文先将盐湖卤水用有机相进行萃取，得到富锂有机相，以富锂有机相作为阴极电解液进行电解，能够使锂富集回收到阳极室的同时生成六氟磷酸锂，采用富锂态电极和贫锂态电极电解时，对锂具有较高的选择性，可以有效的避免其他杂质离子被萃取到有机相中，防止杂质离子进入到阳极室，电解时，富锂有机相的锂离子嵌入到贫锂态电极中，富锂态电极锂离子则脱出进入阳极电解液中，交换后，贫锂态电极嵌入的锂离子脱出，阴极室离子液体中的[PF6]-通过膜进入阳极室的有机溶液中形成LiPF6电解质盐。
示例性的，所述的电解装置为本领域常规的电解装置，例如电解槽。
在一实施例中，所述有机相与盐湖卤水的体积比为(0.5～4)：1；将有机相、盐湖卤水的体积比控制在此范围内，能够有效的富集盐湖卤水中的锂。
在一实施例中，所述有机相与盐湖卤水的体积比为(1～2)：1。将有机相、盐湖卤水的体积比控制在此范围内，能够有效的富集盐湖卤水中的锂，同时分相速度以及萃取速度较好。
在一实施例中，所述萃取剂与六氟磷酸盐离子液体的体积比为(5～30)：(60～95)。
在一实施例中，所述萃取剂与六氟磷酸盐离子液体的体积比为(10～30)：(60～95)。
在一实施例中，所述萃取剂与六氟磷酸盐离子液体的体积比为(10～20)：(80～90)。
在一实施例中，所述萃取剂为磷酸三丁酯。
在一实施例中，所述六氟磷酸盐离子液体为1-丁基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐中的至少一种。
本文以磷酸三丁酯为萃取剂，对锂有高选择性和高萃取率，不会发生乳化 现象，避免使用氯化铁共萃剂，不需要将卤水进行酸化处理，本文在萃取后直接电解，避免了后续进行的反萃过程使用大量高浓度酸性液体对设备的破坏，简化萃取工艺流程。
其中，六氟磷酸盐离子液体的性质稳定的同时，能够为体系提供[PF6]-，进而能够与贫锂态电极脱出的锂离子，在阴极室离子液体形成LiPF6电解质盐。
在一实施例中，所述膜包括阴离子交换膜。
在一实施例中，所述富锂态电极为LiMn2O4电极、LiFePO4电极、Li2TiO3电极、Li7Ti5O12电极、LiNixCoyMn1-x-yO2电极中的至少一种；
其中，0＜x＜1，0＜y＜1。
其中，具有代表性的LiNixCoyMn1-x-yO2电极为LiNi1/3Co1/3Mn1/3O2(简称NCM333)电极。
示例性的，以LiFePO4电极为例说明富锂态电极的制备方法：将LiFePO4、导电剂、粘结剂按照质量比(70～85)：(8～15)：(8～15)混合均匀后，涂敷于集流体表面，干燥，即得LiFePO4电极。
示例性的，涂覆量为10～30mg/cm2。
示例性的，导电剂为炭黑、乙炔黑、碳纳米管、石墨烯中的至少一种。
示例性的，粘结剂为PVDF。
当为LiMn2O4电极、Li2TiO3电极、Li7Ti5O12电极、LiNixCoyMn1-x-yO2电极时，只需将LiFePO4替换成相对应的LiMn2O4、Li2TiO3、Li7Ti5O12、LiNixCoyMn1-x-yO2即可。
在一实施例中，所述贫锂态电极为Li1-aMnO4电极、Li1-aFePO4电极、Li2-bTiO3电极、Li7-cTi5O12电极、Li1-aNixCoyMn1-x-yO2电极中的至少一种；
其中，0＜a＜1，0＜b＜2，0＜c＜7。
示例性的，以Li1-aFePO4电极为例说明贫锂态电极的制备方法：以上述制备得到的LiFePO4电极为正极，AgCl电极作为负极，置于电解液中，以恒定的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li1-aFePO4电极。
本文首先以富锂态电极阳极，以贫锂态电极为阴极，在电解过程中，富锂有机相的锂离子嵌入到贫锂态电极中，富锂态电极锂离子则脱出进入阳极电解液中，交换后，贫锂态电极嵌入的锂离子脱出，阴极室离子液体中的[PF6]-通过膜进入阳极室的有机溶液中形成LiPF6电解质盐。
在一实施例中，所述六氟磷酸锂溶液包括六氟磷酸锂和有机溶剂。
在一实施例中，所述六氟磷酸锂溶液中六氟磷酸锂的浓度为20～100mmol/L。
在一实施例中，所述六氟磷酸锂溶液中六氟磷酸锂的浓度为40～60mmol/L。
在一实施例中，所述有机溶剂为碳酸二甲酯、酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸甲乙酯中的至少一种。以括碳酸二甲酯、酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸甲乙酯为有机溶剂，电解后，阳极室的溶液为高纯度的六氟磷酸锂和有机溶剂的混合液，阳极室的溶液可直接用于二次电池的电解液。
在一实施例中，所述电解的电压为1～4V。
本文的有益效果在于：(1)本文先将盐湖卤水用有机相进行萃取，得到富锂有机相，以富锂有机相作为阴极电解液进行电解，能够使锂富集回收到阳极室的同时生成六氟磷酸锂，采用富锂态电极和贫锂态电极电解时，对锂具有较高的选择性，可以有效的避免其他杂质离子被萃取到有机相中，防止杂质离子进入到阳极室，电解时，富锂有机相的锂离子嵌入到贫锂态电极中，富锂态电极锂离子则脱出进入阳极电解液中，交换后，贫锂态电极嵌入的锂离子脱出，阴极室离子液体中的[PF6]-通过膜进入阳极室的有机溶液中形成LiPF6电解质盐；(2)本文的有机相中的萃取剂和六氟磷酸盐离子液体，对锂有高选择性和高萃取率，不会发生乳化现象，避免使用氯化铁共萃剂，不需要将卤水进行酸化处理，本文在萃取后直接电解，避免了后续进行的反萃过程使用大量高浓度酸性液体对设备的破坏，简化萃取工艺流程。
具体实施方式
为了更好地说明本文的目的、技术方案和优点，下面将结合具体实施例及对比例对本文作进一步说明，其目的在于详细地理解本文的内容，而不是对本文的限制。
本文实施所涉及的实验试剂及仪器，除非特别说明，均为常用的普通试剂及仪器。
实施例1
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将LiFePO4、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得LiFePO4富锂 态电极。
(2)制备贫锂态电极：以步骤(1)的LiFePO4富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的的NaCl电解液中，以1.1V的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li1-aFePO4贫锂态电极。
(3)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(4)将六氟磷酸锂和碳酸二甲酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将LiFePO4富锂态电极置于阳极室中作为阳极，将Li1-aFePO4贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施加2V的电压，在室温下电解1.5h；
(6)将LiFePO4富锂态电极、Li1-aFePO4贫锂态电极取出后冲洗，而后将二者位置互换(即将LiFePO4富锂态电极置于阴极室中，将Li1-aFePO4贫锂态电极置于阳极室中)，向阴阳极施加2V的电压，在室温下电解1.5h，阳极室溶液即为LiPF6电解质盐。
实施例2
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将LiMn2O4、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得LiMn2O4富锂态电极。
(2)制备贫锂态电极：以步骤(1)的LiMn2O4富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的NaCl电解液中，以1.1V的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li1-aMn2O4贫锂态电极。
(3)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比90：10混 合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1：1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(4)将六氟磷酸锂、碳酸二甲酯和碳酸乙烯酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液，碳酸二甲酯和碳酸乙烯酯的体积比为2:1；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将LiMn2O4富锂态电极置于阳极室中作为阳极，将Li1-aMn2O4贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施加2.3V的电压，在室温下电解1h；
(6)将LiMn2O4富锂态电极、Li1-aMn2O4贫锂态电极取出后冲洗，而后将二者位置互换(即将LiMn2O4富锂态电极置于阴极室中，将Li1-aMn2O4贫锂态电极置于阳极室中)，向阴阳极施加2.3V的电压，在室温下电解1h，阳极室溶液即为LiPF6电解质盐。
实施例3
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将LiNi1/3Co1/3Mn1/3O2、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得LiNi1/3Co1/3Mn1/3O2富锂态电极。
(2)制备贫锂态电极：以步骤(1)的LiNi1/3Co1/3Mn1/3O2富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的NaCl电解液中，以1.1V的电压进行脱锂，当电流低至0.2mA即停止反应，得到LiNi1-dCo1/3Mn1/3O2贫锂态电极。
(3)将磷酸三丁酯和1-己基-3-甲基咪唑六氟磷酸盐按照体积比80：20混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比2：1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(4)将六氟磷酸锂、碳酸二甲酯和碳酸甲乙酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液，碳酸二甲酯和碳酸甲乙酯的体积比为1:1；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将LiNi1/3Co1/3Mn1/3O2富锂态电极置于阳极室中作为阳极，将LiNi1-dCo1/3Mn1/3O2贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施加1V的电压，在室温下电解2h；
(6)将LiNi1/3Co1/3Mn1/3O2富锂态电极、LiNi1-dCo1/3Mn1/3O2贫锂态电极取出后冲洗，而后将二者位置互换(即将LiNi1/3Co1/3Mn1/3O2富锂态电极置于阴极室中，将LiNi1-dCo1/3Mn1/3O2贫锂态电极置于阳极室中)，向阴阳极施加1V的电压，在室温下电解2h，阳极室溶液即为LiPF6电解质盐。
实施例4
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将LiFePO4、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得LiFePO4富锂态电极。
(2)制备贫锂态电极：以步骤(1)的LiFePO4富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的的NaCl电解液中，以1.1V的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li1-aFePO4贫锂态电极。
(3)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+0.55g/L、Na+49.39g/L、Mg2+122.42g/L、K+16.97g/L、B 5.37g/L、Cl-72.19g/L。
(4)将六氟磷酸锂和碳酸二甲酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将LiFePO4富锂态电极置于阳极室中作为阳极，将Li1-aFePO4贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施 加2V的电压，在室温下电解1.5h；
(6)将LiFePO4富锂态电极、Li1-aFePO4贫锂态电极取出后冲洗，而后将二者位置互换(即将LiFePO4富锂态电极置于阴极室中，将Li1-aFePO4贫锂态电极置于阳极室中)，向阴阳极施加2V的电压，在室温下电解1.5h，阳极室溶液即为LiPF6电解质盐。
实施例5
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将Li2TiO3、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得Li2TiO3富锂态电极。
(2)制备贫锂态电极：以步骤(1)的Li2TiO3富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的的NaCl电解液中，以1.1V的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li2-bTiO3贫锂态电极。
(3)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(4)将六氟磷酸锂和碳酸二甲酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将Li2TiO3富锂态电极置于阳极室中作为阳极，将Li2-bTiO3贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施加2V的电压，在室温下电解1.5h；
(6)将Li2TiO3富锂态电极、Li2-bTiO3贫锂态电极取出后冲洗，而后将二者位置互换(即将Li2TiO3富锂态电极置于阴极室中，将Li2-bTiO3贫锂态电极置于阳极室中)，向阴阳极施加2V的电压，在室温下电解1.5h，阳极室溶液即为LiPF6电解质盐。
对比例1
一种制备电解质盐的方法，包括以下步骤：
(1)制备富锂态电极：将LiFePO4、炭黑、PVDF按照质量比80：10：10混合均匀后，以15mg/cm2的涂敷量涂覆于碳布表面，干燥，即得LiFePO4富锂态电极。
(2)制备贫锂态电极：以步骤(1)的LiFePO4富锂态电极为正极，AgCl电极作为负极，置于0.5mol/L的的NaCl电解液中，以2V的电压进行脱锂，当电流低至0.2mA即停止反应，得到Li1-aFePO4贫锂态电极。
(3)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(4)将六氟磷酸锂和碳酸二甲酯配制成六氟磷酸锂浓度为50mmol/L的六氟磷酸锂溶液；
(5)用阴离子交换膜将电解槽分割成阳极室和阴极室，将LiFePO4富锂态电极置于阳极室中作为阳极，将Li1-aFePO4贫锂态电极置于阴极室中作为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，向阴阳极施加2V的电压，在室温下电解1.5h，阳极室溶液即为LiPF6电解质盐。
对比例2
对比例2在萃取后，用盐酸反萃取。
一种制备电解质盐的方法，包括以下步骤：
(1)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+1.59g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(2)将0.5mol/L的盐酸溶液加入萃取后的富锂有机相，盐酸溶液与富锂有机相的体积比为1:1，在恒温振荡器上振荡30min，静置分相，得到反萃有机相。
对比例3
对比例3在萃取后，用盐酸反萃取。
一种制备电解质盐的方法，包括以下步骤：
(1)将磷酸三丁酯和1-丁基-3-甲基咪唑六氟磷酸盐按照体积比85:15混合均匀，得到有机相，以盐湖卤水为水相，将有机相和水相按照体积比1.5:1置于恒温震荡器上进行振荡30min混合均匀，静置20min，离心分离，得到富锂有机相；
盐湖卤水中所含离子浓度(g/L)分别为：Li+0.55g/L、Na+98.56g/L、Mg2+92.47g/L、K+20.33g/L、B 6.03g/L、Cl-273.1g/L。
(2)将1mol/L的盐酸溶液加入萃取后的富锂有机相，盐酸溶液与富锂有机相的体积比为1:1，在恒温振荡器上振荡30min，静置分相，得到反萃有机相。
测试例
性能检测：使用电感耦合等离子体发生光谱仪(ICP)测试实施例1～5、对比例1的富锂有机相和LiPF6电解质盐以及对比例1、2的富锂有机相和反萃有机相的锂离子浓度和其他杂质浓度如表1所示。
表1

从表1中可看出，本文实施例的LiPF6电解质盐中，锂的纯度高达98％以上，说明经本文的方法处理后，所得到的LiPF6电解质盐中杂质离子含量极少，LiPF6电解质盐纯度高，且对比对比例2、3的传统反萃方法，本文的电解效果要显著的优于反萃。

Claims (15)

  1. 一种制备电解质盐的方法，其特征在于，包括以下步骤：
    用有机相萃取盐湖卤水，得到富锂有机相，所述有机相包括萃取剂和六氟磷酸盐离子液体；
    提供包括阳极室和阴极室的电解装置，以富锂态电极为阳极，以贫锂态电极为阴极，以六氟磷酸锂溶液为阳极电解液，以富锂有机相作为阴极电解液，进行电解；
    将富锂态电极和贫锂态电极位置互换，再进行电解，在阳极室形成六氟磷酸锂电解质盐。
  2. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述有机相与盐湖卤水的体积比为(0.5～4)：1。
  3. 根据权利要求2所述的制备电解质盐的方法，其特征在于，所述有机相与盐湖卤水的体积比为(1～2)：1。
  4. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述萃取剂与六氟磷酸盐离子液体的体积比为(5～30)：(60～95)。
  5. 根据权利要求4所述的制备电解质盐的方法，其特征在于，所述萃取剂与六氟磷酸盐离子液体的体积比为(10～30)：(60～95)。
  6. 根据权利要求4所述的制备电解质盐的方法，其特征在于，所述萃取剂、六氟磷酸盐离子液体的体积比为(10～20)：(80～90)。
  7. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述萃取剂为磷酸三丁酯。
  8. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述六氟磷酸盐离子液体为1-丁基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐中的至少一种。
  9. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述富锂态电 极为LiMn2O4电极、LiFePO4电极、Li2TiO3电极、Li7Ti5O12电极、LiNixCoyMn1-x-yO2电极中的至少一种；
    其中，0＜x＜1，0＜y＜1。
  10. 根据权利要求9所述的制备电解质盐的方法，其特征在于，所述贫锂态电极为Li1-aMnO4电极、Li1-aFePO4电极、Li2-bTiO3电极、Li7-cTi5O12电极、Li1-aNixCoyMn1-x-yO2电极中的至少一种；
    其中，0＜a＜1，0＜b＜2，0＜c＜7。
  11. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述六氟磷酸锂溶液包括六氟磷酸锂和有机溶剂。
  12. 根据权利要求11所述的制备电解质盐的方法，其特征在于，所述六氟磷酸锂溶液中六氟磷酸锂的浓度为20～100mmol/L。
  13. 根据权利要求11所述的制备电解质盐的方法，其特征在于，所述六氟磷酸锂溶液中六氟磷酸锂的浓度为40～60mmol/L。
  14. 根据权利要求13所述的制备电解质盐的方法，其特征在于，所述有机溶剂为碳酸二甲酯、酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸甲乙酯中的至少一种。
  15. 根据权利要求1所述的制备电解质盐的方法，其特征在于，所述电解的电压为1～4V。
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