WO2024254863A1 - 锂离子筛颗粒的制备方法及其应用 - Google Patents

锂离子筛颗粒的制备方法及其应用 Download PDF

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WO2024254863A1
WO2024254863A1 PCT/CN2023/100789 CN2023100789W WO2024254863A1 WO 2024254863 A1 WO2024254863 A1 WO 2024254863A1 CN 2023100789 W CN2023100789 W CN 2023100789W WO 2024254863 A1 WO2024254863 A1 WO 2024254863A1
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ion sieve
lithium ion
preparation
lithium
particles
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French (fr)
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李爱霞
余海军
谢英豪
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/CN2023/100789 priority Critical patent/WO2024254863A1/zh
Priority to CN202380010020.4A priority patent/CN117015436B/zh
Priority to ARP240101207A priority patent/AR132670A1/es
Publication of WO2024254863A1 publication Critical patent/WO2024254863A1/zh
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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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention belongs to the technical field of lithium extraction from salt lakes, and in particular relates to a preparation method of lithium ion sieve particles and application thereof.
  • Salt lake lithium resources account for more than 69% of the world's industrial lithium reserves.
  • the world's salt lake lithium resources are mainly distributed in South America, North America and Asia. Salt lake areas are often sparsely populated, with incomplete infrastructure and insufficient energy supply, which has brought serious constraints to the development and utilization of these lithium resources.
  • the main methods for extracting lithium from brine include evaporation crystallization, precipitation, extraction, adsorption, calcination, membrane separation and other methods.
  • the adsorption method is to separate and extract lithium using lithium selective adsorbents, which is particularly suitable for salt lake brine with high Mg/Li.
  • the key to this method lies in the selection of adsorbent materials.
  • adsorbent materials can be summarized into two categories: organic adsorbents and inorganic adsorbents.
  • Organic adsorbents usually use strong acidic cation exchange resins to selectively collect and recover lithium from lithium-containing solutions, mainly relying on Coulomb force to adsorb lithium ions into the resin, but this type of adsorbent has a low affinity for lithium ions and low selectivity for lithium ions, making it unsuitable for lithium extraction and recovery.
  • inorganic lithium adsorbents mainly relies on the unique memory effect and selectivity of inorganic lithium ion adsorbents for Li +. It has the advantages of low cost, good cycle stability and high selectivity, and has become the most promising adsorbent for adsorbing lithium ions from lithium-containing solutions. According to the classification of the main elements in inorganic lithium ion adsorbent materials, they mainly include aluminum salt adsorbents, antimony acid adsorbents, titanium oxide adsorbents and manganese oxide adsorbents.
  • lithium ion sieve materials Although these lithium ion sieve materials have the advantages of large adsorption capacity, high selectivity, and good cycle stability, they usually exist in powder form. They have poor fluidity, low cycle efficiency, and are easy to lose in industrial applications. In addition, powdered ion sieve materials can cause a large pressure drop, resulting in high energy consumption in column operations. They cannot be directly used to extract lithium from salt lake brine. These shortcomings are currently mainly overcome through the granulation molding technology of powder lithium ion sieve. The granulation method is to evenly mix the lithium ion sieve powder and the adhesive polymer together, and then form spherical particles through the polymerization reaction of the binder itself.
  • the powder ion sieve can have good mechanical strength, so that it can adapt to industrial column operations, effectively improving the recycling and permeability of the lithium ion sieve powder.
  • PVC, PVDF, etc. as the binder
  • the material mechanical properties of the agent are excellent, acid and alkali resistant, easy to shape and low cost, but compared with the powder adsorbent, the adsorption performance of the ion sieve particles after granulation will be significantly reduced. This is because PVC and PVDF binders are hydrophobic materials, which reduce the diffusion capacity of lithium ions.
  • binders containing hydrophilic groups such as agar, chitosan, polyacrylonitrile, and polyacrylamide are used to granulate powders to improve the permeability and wettability of adsorbed water and improve the adsorption performance, but hydrophilic binders have low stability in water and poor mechanical properties, which reduces the cycle performance of the adsorbent and is not suitable for long-term use.
  • the present disclosure aims to at least solve the technical problems existing in the above-mentioned prior art. To this end, the present disclosure provides a preparation method of lithium ion sieve particles and application thereof.
  • a method for preparing lithium ion sieve particles comprising the following steps:
  • the lithium ion sieve powder is a titanium-based lithium ion sieve, a manganese-based lithium ion sieve, or an aluminum-based lithium ion sieve.
  • the binder is at least one of PVDF, PVC or epoxy resin.
  • the pore-forming agent is at least one of ethanol, isopropanol or n-butanol.
  • the pore-forming agent is a volatile organic compound, and the high temperature environment accompanying the extrusion process allows the pore-forming agent to volatilize quickly and generate gas, so that the extruded particles have a porous structure, and the porous structure has strong liquid absorption.
  • step S1 the extrusion granulation is performed using an extruder, and the segmented temperature range of the extruder is 110-250°C.
  • step S1 the mass ratio of the lithium ion sieve powder to the pore-forming agent is 1:(0.1-0.2).
  • step S1 the mass ratio of the lithium ion sieve powder to the binder is 1:(0.15-0.3).
  • the porous particles in step S1, have a particle size of 1-5 mm.
  • the strong oxidizing solution is at least one of nitric acid, sodium hypochlorite, hydrogen peroxide, ammonium persulfate, acidic potassium permanganate, acidic potassium dichromate or potassium persulfate.
  • step S2 the temperature of the first heating treatment is 70-90° C. and the time is 3-6 hours.
  • step S2 the length of the carbon fiber filaments is 0.1-2 mm.
  • step S3 the temperature of the second heating treatment is 60-80° C. and the time is 2-4 hours.
  • step S3 the temperature of the third heating treatment is 90-110° C., and the time is 1-3 hours.
  • the silane coupling agent is at least one of 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane.
  • step S3 the mass content of carbon fiber filaments in the lithium ion sieve particles is 1%-10%.
  • the present disclosure also provides application of the lithium ion sieve particles prepared by the preparation method in extracting lithium from salt lakes.
  • the present invention uses a strong oxidizing solution to oxidize and etch the surface of carbon fiber filaments, introduces oxygen-active functional groups (such as hydroxyl and carboxyl), can improve the hydrophilicity of carbon fiber filaments, reduce the surface tension of carbon fiber filaments, and make them easy to disperse evenly in the solution without attracting each other and affecting the processing performance.
  • oxygen-active functional groups such as hydroxyl and carboxyl
  • the oxidized carbon fiber is first combined with a silane coupling agent and then Branched to the surface of lithium ion sieve particles, silane coupling is used as a bridging agent between carbon fiber filaments and lithium ion sieve particles, and its silane alkoxy end reacts with the oxygen-active functional group of carbon fiber filaments, and the organic functional group end combines with the hydrophobic binder in the lithium ion sieve particles, so that there are covalent bonds, hydrogen bonds and multiple interface bonding effects in the interface area, which plays a good bridging role, thereby improving the interface strength between carbon fiber and lithium ion sieve particles.
  • the present disclosure is through the access of carbon fiber filaments on the surface of lithium ion sieve particles, the carbon fiber filaments can disturb the solution near the lithium ion sieve particles, enhance the convection mass transfer effect near the lithium ion sieve particles, and make the lithium-containing solution near the lithium ion sieve particles more smoothly and quickly enter the pores of the particles, improve the problem of hydrophobic binders reducing the diffusion capacity of lithium ions, and improve the diffusion capacity of lithium ions in the solution through the disturbance of carbon fiber filaments on the surface of particles, thereby improving the adsorption efficiency of lithium ion sieve particles.
  • hydrophobic binders Compared with hydrophilic binders, hydrophobic binders have higher stability in water and better mechanical properties, and are suitable for the recycling of lithium ion sieve particles.
  • the polar groups introduced into the carbon fiber after surface treatment enhance the hydrophilicity, which can further improve the permeability and wettability of the lithium ion sieve particles in the solution, thereby improving the adsorption efficiency.
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • Manganese lithium ion sieve powder MnO2 ⁇ 0.5H2O , PVDF, and isopropanol were mixed in a mass ratio of 1:0.15:0.15, and then extruded and granulated using a twin-screw extruder.
  • the first section temperature of the extruder was 130°C
  • the second section temperature was 170°C
  • the third section temperature was 190°C
  • the fourth section temperature was 210°C
  • the die head temperature was 230°C.
  • the extruded strips were pelletized using a pelletizer to obtain porous particles with a particle size D50 of 4.0 mm.
  • This embodiment prepares a lithium ion sieve particle, and the specific process is as follows:
  • This comparative example prepares a lithium ion sieve particle.
  • the difference from Example 1 is that only step (1) of Example 1 is performed, and the obtained porous particle is the lithium ion sieve particle of this comparative example.
  • the adsorption performance of the lithium ion sieve particles prepared in the above embodiments and comparative examples was tested.
  • the test method is as follows: 300 g of the lithium ion sieve particles of the embodiments and comparative examples were weighed and filled into an adsorption column, 10 kg of brine was weighed, and adsorption was performed through the column at a rate of 5 seconds per drop, the lithium content after passing through the column was tested, and the lithium adsorption capacity was calculated. The results are shown in Table 2.
  • adsorption capacity (lithium content in brine before adsorption - lithium content in brine after adsorption) * mass of brine passing through the column / mass of lithium ion sieve particles.

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Abstract

本公开属于盐湖提锂技术领域，公开了一种锂离子筛颗粒的制备方法及其应用，将锂离子筛粉体、粘结剂、造孔剂混合后进行挤出造粒，得到多孔颗粒物；将碳纤维丝置于强氧化性溶液中进行第一次加热处理，取出碳纤维丝并清洗干燥，得到改性碳纤维丝；将改性碳纤维丝置于硅烷偶联剂溶液中进行第二次加热处理，得到悬浊液，往悬浊液中加入多孔颗粒物混匀，进行第三次加热处理，经过滤、干燥，即得锂离子筛颗粒。

Description

锂离子筛颗粒的制备方法及其应用 技术领域
本公开属于盐湖提锂技术领域，具体涉及一种锂离子筛颗粒的制备方法及其应用。
背景技术
盐湖锂资源占世界锂资源工业储量的69％以上，世界盐湖锂资源主要分布于南美，北美和亚洲；盐湖地区往往人口稀少，基础设施尚不完善，能源供应不充足，因此给开发利用这些锂资源带来了严重的制约。从卤水中提取锂的方法主要有蒸发结晶法、沉淀法、萃取法、吸附法、煅烧法、膜分离法等多种方法。
其中，吸附法是利用锂选择性吸附剂分离和提取锂，尤其适用于高Mg/Li的盐湖卤水，该方法的关键在于吸附剂材料的选择。通常，吸附剂材料可归纳为有机吸附剂和无机吸附剂两大类，有机吸附剂通常使用强酸性阳离子交换树脂从含锂溶液中选择性地收集和回收锂，主要依靠库仑力将锂离子吸附到树脂中，但该类吸附剂对锂离子的亲和力较低，对锂离子的选择性不高，不适合用于锂的提取和回收。无机锂吸附剂的工作原理主要是依赖于无机锂离子吸附剂对Li+的独特记忆效应和选择性，具有成本低、循环稳定性好和选择性高等优点，已成为了从含锂溶液中吸附锂离子的最有应用前景的吸附剂。按照无机锂离子吸附剂材料中主元素的分类，主要包括铝盐吸附剂、锑酸型吸附剂、钛氧化物吸附剂和锰氧化物吸附剂。
这些锂离子筛材料虽然具有吸附容量大、选择性高、循环稳定性好等优势，但是它们通常以粉末形式存在，其在工业应用中流动性差，循环效率低，易损失，并且粉末态离子筛材料可导致大的压降，造成柱式操作中的高能量消耗，不能直接用于盐湖卤水中提锂，这些缺点目前主要通过粉体锂离子筛的造粒成型技术来克服。造粒法是将锂离子筛粉体和具有粘接性的高分子聚合物均匀地混合在一起，再通过粘结剂本身的聚合反应成球形颗粒，通过造粒，可以使粉体离子筛具有良好的机械强度，从而能够适应工业柱式操作，有效地提高锂离子筛粉体的回收利用了和渗透性能。以PVC、PVDF等为粘结 剂的材料力学性能优异，耐酸碱，易于成型且成本低廉，但与粉末吸附剂相比，造粒后的离子筛颗粒吸附性能会明显下降，这是因为PVC、PVDF粘结剂为疏水材料，降低了锂离子的扩散能力。也有相关报道使用含有亲水基团的粘结剂如琼脂、壳聚糖、聚丙烯腈、聚丙烯酰胺对粉体进行造粒成型，通过提高吸附水的渗透性和润湿性，提高吸附性能，但亲水性粘结剂在水中的稳定性较低，机械性能差，降低了吸附剂的循环性能，不适合长期使用。
发明内容
本公开旨在至少解决上述现有技术中存在的技术问题。为此，本公开提出一种锂离子筛颗粒的制备方法及其应用。
根据本公开的一个方面，提出了一种锂离子筛颗粒的制备方法，包括以下步骤：
S1：将锂离子筛粉体、粘结剂、造孔剂混合后进行挤出造粒，得到多孔颗粒物；
S2：将碳纤维丝置于强氧化性溶液中进行第一次加热处理，取出碳纤维丝并清洗干燥，得到改性碳纤维丝；
S3：将所述改性碳纤维丝置于硅烷偶联剂溶液中进行第二次加热处理，得到悬浊液，往所述悬浊液中加入所述多孔颗粒物混匀，进行第三次加热处理，经过滤、干燥，即得所述锂离子筛颗粒。
在本公开的一些实施方式中，步骤S1中，所述锂离子筛粉体为钛系锂离子筛、锰系锂离子筛或铝系锂离子筛。
在本公开的一些实施方式中，步骤S1中，所述粘结剂为PVDF、PVC或环氧树脂中的至少一种。
在本公开的一些实施方式中，步骤S1中，所述造孔剂为乙醇、异丙醇或正丁醇中的至少一种。造孔剂为挥发性有机物，利用挤出过程伴随的高温环境，使得造孔剂快速挥发产气，使挤出颗粒具有多孔隙结构，多孔结构具有较强的吸液性。
在本公开的一些实施方式中，步骤S1中，所述挤出造粒采用挤出机进行，挤出机的分段温度范围为110-250℃。
在本公开的一些实施方式中，步骤S1中，所述锂离子筛粉体与造孔剂的质量比为1:(0.1-0.2)。
在本公开的一些实施方式中，步骤S1中，所述锂离子筛粉体与粘结剂的质量比为1：(0.15-0.3)。
在本公开的一些实施方式中，步骤S1中，所述多孔颗粒物粒径为1-5mm。
在本公开的一些实施方式中，步骤S2中，所述强氧化性溶液为硝酸、次氯酸钠、过氧化氢、过硫酸铵、酸性高锰酸钾、酸性重铬酸钾或过硫酸钾中的至少一种。
在本公开的一些实施方式中，步骤S2中，所述第一次加热处理的温度为70-90℃，时间为3-6h。
在本公开的一些实施方式中，步骤S2中，所述碳纤维丝的长度为0.1-2mm。
在本公开的一些实施方式中，步骤S3中，所述第二次加热处理的温度为60-80℃，时间为2-4h。
在本公开的一些实施方式中，步骤S3中，所述第三次加热处理的温度为90-110℃，时间为1-3h。
在本公开的一些实施方式中，步骤S3中，所述硅烷偶联剂为3-氨基丙基三乙氧基硅烷或3-氨基丙基三甲氧基硅中的至少一种。
在本公开的一些实施方式中，步骤S3中，所述硅烷偶联剂溶液是按照硅烷偶联剂：无水乙醇质量比＝1:(4-5)超声分散配制得到。
在本公开的一些实施方式中，步骤S3中，所述锂离子筛颗粒中碳纤维丝的质量含量为1％-10％。
本公开还提供所述的制备方法制得的所述锂离子筛颗粒在盐湖提锂中的应用。
根据本公开的实施方式，至少具有以下有益效果：
本公开利用强氧化性溶液对碳纤维丝进行表面氧化刻蚀，引入氧活性官能团(如羟基和羧基)，可以提升碳纤维丝的亲水性，降低碳纤维丝的表面张力，易于在溶液中分散均匀而不会彼此吸引影响加工性能，氧化处理后的碳纤维先与硅烷偶联剂结合，再接 枝到锂离子筛颗粒表面，硅烷偶联作为碳纤维丝和锂离子筛颗粒的架桥剂，其硅烷氧基端与碳纤维丝的氧活性官能团反应，有机官能基端与锂离子筛颗粒中的疏水性粘结剂结合，使界面区存在共价键、氢键多种界面键合作用，起到良好的桥接作用，从而能够提高碳纤维与锂离子筛颗粒的界面强度。本公开通过在锂离子筛颗粒表面接入碳纤维丝，碳纤维丝可以扰动锂离子筛颗粒附近的溶液，增强锂离子筛颗粒附近的对流传质作用，使锂离子筛颗粒附近的含锂溶液更加顺畅快速的进入颗粒的孔隙中，改善疏水性粘结剂降低锂离子扩散能力的问题，通过颗粒表面碳纤维丝对溶液的扰动提高溶液中锂离子的扩散能力，进而提高锂离子筛颗粒的吸附效率。与亲水性粘结剂相比，疏水性粘结剂在水中的稳定性更高，机械性能更好，适于锂离子筛颗粒的循环使用。此外碳纤维经表面处理后引入的极性基团提升了亲水性，能进一步提高锂离子筛颗粒在溶液中的渗透性和润湿性，从而提升吸附效率。
具体实施方式
以下将结合实施例对本公开的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本公开的目的、特征和效果。
实施例1
本实施例制备了一种锂离子筛颗粒，具体过程为：
(1)将锰系锂离子筛粉体MnO2·0.5H2O、PVDF、乙醇按质量比1：0.2：0.1混合后，使用双螺杆挤出机进行挤出造粒，挤出机第一段温度130℃，第二段温度170℃，第三段温度190℃，第四段温度210℃，模头温度230℃，挤出后用切粒机将挤出条切粒得到粒径D50为2.3mm的多孔颗粒物。
(2)将长度约为0.5mm的碳纤维丝浸泡在2mol/L的硝酸溶液中，在85℃下回流4h，对碳纤维丝进行表面氧化处理，取出碳纤维并清洗干燥，得到改进碳纤维丝。
(3)将改进碳纤维丝置于3-氨基丙基三乙氧基硅烷溶液(3-氨基丙基三乙氧基硅烷：无水乙醇溶液质量比＝1:4)中，在75℃下回流2.5h，降至室温，再往上述悬浊液中加入步骤(1)的多孔颗粒物混匀，在100℃下回流1.5h，反应结束后过滤，干燥，得到表面附着有碳纤维的锂离子筛颗粒，产物锂离子筛颗粒中碳纤维的质量含量为4％。
实施例2
本实施例制备了一种锂离子筛颗粒，具体过程为：
(1)将锰系锂离子筛粉体MnO2·0.5H2O、PVDF、异丙醇按质量比1：0.15：0.15混合后，使用双螺杆挤出机进行挤出造粒，挤出机第一段温度130℃，第二段温度170℃，第三段温度190℃，第四段温度210℃，模头温度230℃，挤出后用切粒机将挤出条切粒得到粒径D50为4.0mm的多孔颗粒物。
(2)将长度约为1mm的碳纤维丝浸泡在2mol/L的硝酸溶液中，在90℃下回流3h，对碳纤维丝进行表面氧化处理，取出碳纤维并清洗干燥，得到改进碳纤维丝。
(3)将改进碳纤维丝置于3-氨基丙基三甲氧基硅烷溶液(3-氨基丙基三甲氧基硅烷：无水乙醇溶液质量比＝1:5)中，在70℃下回流5h，降至室温，再往上述悬浊液中加入步骤(1)的多孔颗粒物混匀，在95℃下回流2h，反应结束后过滤，干燥，得到表面附着有碳纤维的锂离子筛颗粒，产物锂离子筛颗粒中碳纤维的质量含量为3％。
实施例3
本实施例制备了一种锂离子筛颗粒，具体过程为：
(1)将锰系锂离子筛粉体MnO2·0.5H2O、PVDF、乙醇按质量比1：0.3：0.1混合后，使用双螺杆挤出机进行挤出造粒，挤出机第一段温度130℃，第二段温度170℃，第三段温度190℃，第四段温度210℃，模头温度230℃，挤出后用切粒机将挤出条切粒得到粒径D50为5mm的多孔颗粒物。
(2)将长度约为1.2mm的碳纤维丝浸泡在1mol/L的次氯酸钠溶液中，在90℃下回流3h，对碳纤维丝进行表面氧化处理，取出碳纤维并清洗干燥，得到改进碳纤维丝。
(3)将改进碳纤维丝置于3-氨基丙基三乙氧基硅烷溶液(3-氨基丙基三乙氧基硅烷：无水乙醇溶液质量比＝1:4)中，在80℃下回流3h，降至室温，再往上述悬浊液中加入步骤(1)的多孔颗粒物混匀，在110℃下回流3h，反应结束后过滤，干燥，得到表面附着有碳纤维的锂离子筛颗粒，产物锂离子筛颗粒中碳纤维的质量含量为7％。
对比例
本对比例制备了一种锂离子筛颗粒，与实施例1的区别在于，只进行实施例1的步骤(1)，所得多孔颗粒物即为本对比例的锂离子筛颗粒。
试验例
对上述实施例及对比例制得的锂离子筛颗粒进行吸附性能测试。测试方法如下：称取实施例和对比例的锂离子筛颗粒300g，填入吸附柱中，称取10kg卤水，以5s每滴的速度过柱进行吸附，测试过柱后锂元素含量，计算出锂吸附容量，结果如表2所示。
其中吸附容量的计算公式如下：吸附容量＝(吸附前卤水中的锂含量-吸附后卤水中的锂含量)*过柱卤水质量/锂离子筛颗粒质量。
表1盐湖卤水中的化学组成
表2锂离子筛颗粒的锂吸附容量和循环吸附性能
由表2可见，实施例的锂吸附容量高于对比例，表明本公开的锂离子筛颗粒经过碳纤维丝接枝后，具有更高的吸附效率。

Claims (16)

  1. 一种锂离子筛颗粒的制备方法，其特征在于，包括以下步骤：
    S1：将锂离子筛粉体、粘结剂、造孔剂混合后进行挤出造粒，得到多孔颗粒物；
    S2：将碳纤维丝置于强氧化性溶液中进行第一次加热处理，取出碳纤维丝并清洗干燥，得到改性碳纤维丝；
    S3：将所述改性碳纤维丝置于硅烷偶联剂溶液中进行第二次加热处理，得到悬浊液，往所述悬浊液中加入所述多孔颗粒物混匀，进行第三次加热处理，经过滤、干燥，即得所述锂离子筛颗粒。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述锂离子筛粉体为钛系锂离子筛、锰系锂离子筛或铝系锂离子筛。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述粘结剂为PVDF、PVC或环氧树脂中的至少一种。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述造孔剂为乙醇、异丙醇或正丁醇中的至少一种。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述锂离子筛粉体与造孔剂的质量比为1:(0.1-0.2)。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述锂离子筛粉体与粘结剂的质量比为1：(0.15-0.3)。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述多孔颗粒物粒径D50为1-5mm。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述强氧化性溶液为硝酸、次氯酸钠、过氧化氢、过硫酸铵、酸性高锰酸钾、酸性重铬酸钾或过硫酸钾中的至少一种。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述第一次加热处理的温度为70-90℃，时间为3-6h。
  10. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述碳纤维丝的长度为0.1-2mm。
  11. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述第二次加热处理的温度为60-80℃，时间为2-4h。
  12. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述第三次加热处理的温度为90-110℃，时间为1-3h。
  13. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述硅烷偶联剂为3-氨基丙基三乙氧基硅烷或3-氨基丙基三甲氧基硅烷中的至少一种。
  14. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述硅烷偶联剂溶液是按照硅烷偶联剂：无水乙醇质量比＝1:(4-5)超声分散配制得到。
  15. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述锂离子筛颗粒中碳纤维丝的质量含量为1％-10％。
  16. 如权利要求1-15任一项所述的制备方法制得的所述锂离子筛颗粒在盐湖提锂中的应用。
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