CN113845143B - Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof - Google Patents
Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of bentonite modified meta-titanic acid type lithium ion sieve precursors, which comprises the following steps: respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution; to Ti (SO) 4 ) 2 Adding precipitant dropwise into the solution to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2‑ Residue; tiO (OH) after washing 2 Diluting the precipitate with water, pulping, and adding C dropwise into the slurry 2 H 7 LiO 4 After the solutions are uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after the dropwise adding is completed; and adding bentonite into the transparent yellow sol, stirring, aging, drying to obtain xerogel, grinding the xerogel, and calcining to obtain the transparent yellow sol. The precursor can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
Description
Technical Field
The invention belongs to the technical field of lithium ion sieves, and particularly relates to a bentonite modified meta-titanic acid type lithium ion sieve precursor and a preparation method thereof.
Background
The method for extracting lithium from salt lake brine generally comprises preparing a proper precursor, and removing Li in the precursor by acid washing + The lithium ion sieve is obtained, so that the synthesis of the titanium lithium ion sieve precursor by adopting a proper method is a key for preparing the lithium ion sieve. At present, the method for synthesizing the titanium lithium ion sieve precursor mainly comprises a high-temperature solid phase method, a hydrothermal method, a sol-gel method, a precipitation peptization method, a template method and the like.
Among them, the precipitation peptization method is an improved method based on the sol-gel method. The preparation method comprises the steps of firstly using a precipitant to enable a titanium source to exist in a precipitation form, then adding a lithium source, complexing the lithium source and the titanium source by using a complexing agent, ageing for a period of time to obtain transparent sol, ageing the colloid at room temperature for a period of time, drying to obtain xerogel, and calcining to obtain the titanium lithium ion sieve precursor. However, the existing lithium ion sieve precursor has small specific surface area and limited adsorption capacity, so that the adsorption effect is general.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bentonite modified meta-titanic acid type lithium ion sieve precursor and a preparation method thereof, and the precursor can effectively solve the problems of small specific surface area and small adsorption capacity of the existing precursor.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of bentonite modified metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Adding precipitant dropwise into the solution to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with water, pulping, and dripping C in step (1) into the slurry 2 H 7 LiO 4 After the solutions are uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after the dropwise adding is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), stirring, aging, drying to obtain xerogel, grinding the xerogel, and calcining to obtain the transparent yellow sol.
In the above scheme, ti (SO 4 ) 2 Is a titanium source, C 2 H 7 LiO 4 Preparing titanium lithium ion sieve precursor sol as a lithium source, adding bentonite into the sol, and calcining to obtain bentonite modified metatitanic acid type lithium ion with uniform mesoporous morphologyThe sub-sieve precursor, bentonite has larger specific surface area, good adsorption performance, large storage capacity and low price, and the bentonite can be inserted into Li when being applied to the precursor modification of the titanium lithium ion sieve 2 TiO 3 In the structure, the metatitanic acid type lithium ion sieve with obviously improved specific surface area and adsorption capacity is prepared, and the lithium extraction efficiency of the traditional lithium ion sieve can be improved.
Further, the precipitant in the step (2) is ammonia water, and the solution is dropwise added to the solution with the pH value of 7-9.
Further, the dropping speed of the precipitant in the step (2) is 8-12 s/drop.
Further, the complexing agent in the step (3) is H with the volume concentration of 25-35% 2 O 2 。
Further, the complexing agent in the step (3) is H with the volume concentration of 30 percent 2 O 2 。
Further, H in step (3) 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 5-7:1.
Further, H in step (3) 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 6:1.
In the above scheme, H 2 O 2 Too small molar ratio with Ti in the mixed solution, resulting in the surface of the prepared sample being in a cracked shape, incomplete, relatively smooth and void-free structure, along with H 2 O 2 The molar ratio of the titanium dioxide to Ti in the mixed solution is increased, the surface of the sample gradually presents a porous structure, when H 2 O 2 When the molar ratio to Ti in the mixed solution is too large, the porosity of the sample surface is rather decreased, and as H 2 O 2 An increase in the amount of Li 2 TiO 3 The intensity of diffraction peak of characteristic crystal face in the crystal is gradually enhanced, which proves that H 2 O 2 The amount of (B) is equal to Li 2 TiO 3 Grain growth is important, H 2 O 2 The main principle of the action is as follows: h 2 O 2 In the preparation process, the catalyst is mainly decomposed into peroxy free radicals (O-O.cndot.) to complex TiO (OH) to obtain TiO (OH) - (O-TiO-O) n-TiO (OH) with stable structure, and then Li is inserted to obtain Li [ Li ] with crystal structure formula 1/3 Ti 2/3 ]O 2 As complexing agent H 2 O 2 When the amount of the organic compound is small, the generated peroxy radical (O-O. Cndot.) is correspondingly reduced, and the effect of complexing TiO (OH) is correspondingly reduced, so that the growth of crystal faces is not favored, and the structure of a sample is incomplete.
Further, the solid-to-liquid ratio of bentonite to transparent yellow sol in the step (4) is 1g:0.5-0.7L.
Further, the solid-to-liquid ratio of bentonite to transparent yellow sol in the step (4) is 1g:0.6L.
In the scheme, with the increase of the solid-to-liquid ratio, the modification treatment of the bentonite is carried out on Li 2 TiO 3 The diffraction crystal face of the precursor has influence, changes towards the direction favorable for the oriented growth of the characteristic crystal face, when the liquid-solid ratio reaches 1g to 0.6L, the intensity of the diffraction peak of the characteristic crystal face is highest, namely the crystal intensity is the highest, the crystallinity is the best, therefore, the Li is more convenient + Is eluted and adsorbed; however, as the amount of bentonite increases, a part of the elements in the bentonite replace Li in the precursor Li2 layer, so that the crystal structure integrity of the precursor decreases, resulting in Li + The elution rate of Li is reduced, the adsorption sites of Li are correspondingly reduced, and Li is reduced + The adsorption capacity of (2) is thus reduced.
Further, after bentonite is added in the step (4), stirring is carried out for 2-4 hours, then aging is carried out for 10-14 hours, and then drying is carried out at 70-90 ℃ to obtain xerogel.
Further, after the xerogel in the step (4) is ground, the temperature is raised to 600-900 ℃ at the speed of 2-4 ℃/min, and the temperature is kept for 1.5-3h.
Further, after the xerogel in the step (4) is ground, the temperature is raised to 750 ℃ at a speed of 3 ℃/min, and the temperature is kept for 2 hours.
In the scheme, as the calcining temperature is increased, the titanium lithium ion sieve precursor is subjected to crystal form transformation to be transformed into beta-monoclinic crystal phase, crystal grains are in a growth trend, the crystal structure is complete, when the temperature reaches 750 ℃, the characteristic diffraction peak of each crystal face reaches the maximum value, and the surface bentonite modified Li 2 TiO 3 Li in the main crystal layer + Fully forming a stable and highly ordered crystal structure whenThe temperature continues to rise, and the intensity of diffraction peaks of each crystal face is reduced instead, which proves that the crystal structure is the most stable when the calcining temperature is 750 ℃.
The beneficial effects of the invention are as follows:
1. the bentonite modified metatitanic acid type lithium ion sieve precursor has higher thermal stability, mainly plays a role in blocking due to the introduction of bentonite, so that the thermal stability of the bentonite modified metatitanic acid type lithium ion sieve precursor is improved.
2. The bentonite modified meta-titanic acid type lithium ion sieve precursor has a porous structure uniformly distributed on the surface, so that the specific surface area of a sample can be increased, the adsorption capacity and the adsorption rate of the lithium ion sieve can be further improved, and the adsorption capacity can reach 45.49mg/g.
3. The bentonite modified metatitanic acid type lithium ion sieve precursor has complete crystal growth and uniformly distributed pore structure on the surface, and is more beneficial to Li + Improving Li + Is an elution equilibrium time of 6 hours, li after 6 hours + The elution rate of the catalyst is as high as 99.85 percent.
Drawings
FIG. 1 is an SEM image of a metatitanic acid type lithium ion sieve precursor prepared in example 1;
FIG. 2 is an SEM image of the meta-titanic acid type lithium ion sieve precursor prepared in comparative example 2;
FIG. 3 is an SEM image of the meta-titanic acid type lithium ion sieve precursor prepared in comparative example 3;
FIG. 4 is an XRD pattern of a lithium-ion meta-titanate screen precursor in example 1;
FIG. 5 is an XRD pattern of the titanate-type lithium ion sieve precursor of example 1 after pickling;
FIG. 6 is an XRD pattern after adsorption of the adsorbent of example 1;
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the drawings.
Example 1
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 8, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 30% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 6:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.6L, stirring for 3 hours, aging for 12 hours, drying at 80 ℃ to obtain xerogel, grinding the xerogel, heating to 750 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 2 hours.
Example 2
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 7, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 25% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 5:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.5L, stirring for 2 hours, aging for 10 hours, drying at 70 ℃ to obtain xerogel, grinding the xerogel, heating to 600 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 2 hours.
Example 3
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 9, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 35% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 7:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.7L, stirring for 4 hours, aging for 14 hours, drying at 90 ℃ to obtain xerogel, grinding the xerogel, heating to 900 ℃ at a speed of 4 ℃/min, calcining, and preserving heat for 2 hours.
Comparative example 1
A preparation method of a metatitanic acid type lithium ion sieve precursor comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 8, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 30% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to the mixed solution is 6:1, the mixture is stirred after the dripping is finished to obtain transparent yellow sol, the transparent yellow sol is aged for 12 hours at room temperature, then dried at 80 ℃ to obtain xerogel, the xerogel is ground, and then the mixture is heated to 750 ℃ at the speed of 3 ℃/min for calcination, and the temperature is kept for 2 hours, thus obtaining the titanium dioxide.
Comparative example 2
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 8, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 30% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 3:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.3L, stirring for 3 hours, aging for 12 hours, drying at 80 ℃ to obtain xerogel, grinding the xerogel, heating to 750 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 2 hours.
Comparative example 3
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 8, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 30% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to the mixed solution is 8:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1 g/1L, stirring for 3 hours, aging for 12 hours, drying at 80 ℃ to obtain xerogel, grinding the xerogel, heating to 750 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 2 hours.
Comparative example 4
A bentonite modified metatitanic acid type lithium ion sieve precursor, the preparation method comprises the following steps:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Dropwise adding ammonia water into the solution, wherein the dropwise adding speed is 10 s/drop, and the pH value of the solution is 8, so as to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with 100ml of water, pulping, and dripping C in the step (1) into the slurry 2 H 7 LiO 4 After the solution is uniformly mixed, H with the volume concentration of 30% is dripped into the mixed solution 2 O 2 ，H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 6:1, and the transparent yellow sol is obtained by stirring after the dripping is completed;
(4) And (3) adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.6L, stirring for 3 hours, aging for 12 hours, drying at 80 ℃ to obtain xerogel, grinding the xerogel, heating to 1000 ℃ at a speed of 3 ℃/min, calcining, and preserving heat for 2 hours.
Test examples
The obtained metatitanic acid type lithium ion sieve precursors in examples 1 to 3 and comparative examples 1 to 4 were acid-washed with 0.2mol/L hydrochloric acid solution, respectively, at 50℃for 6 hours, with a molar ratio of hydrogen ions in the hydrochloric acid to lithium ions in the precursor of 1:1, and the acid-washed precursors were dried to obtain different adsorbents.
1. Respectively carrying out adsorption tests on different adsorbents and lithium hydroxide solution with the concentration of 2g/L according to the solid-to-liquid ratio of 2g to 100ml, wherein the adsorption time is 24 hours, measuring the concentration of lithium ions in the adsorbed solution after adsorption equilibrium, calculating the adsorption capacity according to the calculated adsorption capacity, and then using 0.204mol/L HCl at the constant temperature of 50 DEG CAfter acid washing for 6 hours, diluting the solution, and measuring Li in the solution by using an atomic absorption spectrophotometer + Content, lithium ion elution rate of each sample was calculated, and specific results are shown in table 1.
Table 1: lithium ion concentration in solution after adsorption by different adsorbents
| Adsorption capacity (mg/g) | Elution Rate (%) | |
| Example 1 | 45.49 | 99.85 |
| Example 2 | 45.12 | 99.45 |
| Example 3 | 44.59 | 99.67 |
| Comparative example 1 | 30.62 | 94.21 |
| Comparative example 2 | 32.35 | 94.98 |
| Comparative example 3 | 31.01 | 95.21 |
| Comparative example 4 | 34.12 | 95.36 |
As can be seen from the data in the above tables, the adsorption capacity and elution rate in examples 1 to 3 were both greater than those in comparative examples 1 to 4.
2. The pore structure characteristics of the different adsorbents were separately determined, and the specific results are shown in table 2.
Table 2: structural features of different samples
As can be seen from the data in the above table, the adsorbents in examples 1 to 3 each have a larger specific surface area than the adsorbents in comparative examples 1 to 4, the adsorbents in examples 1 to 3 each have a much smaller pore size than the adsorbents in comparative examples 1 to 4, and the adsorbents in examples 1 to 3 each have a larger adsorption capacity than the adsorbents in comparative examples 1 to 4.
As can be seen from fig. 1 to 3, the sample surface of example 1 has a uniform pore structure; the surface pore structure of the samples of comparative examples 2 and 3 is less.
As can be seen from fig. 4 to 6, the sample before pickling has a complete structure, and the surface of the sample has a uniform porous structure; the structure of the acid-washed sample is destroyed, and the phenomenon of grain polymerization is obvious, because Li with larger radius after acid washing + By H of smaller radius + The crystal structure is changed, the interplanar spacing is reduced, the unit cell volume is contracted, the ion arrangement is destroyed, and the lattice energy is improvedRise, eventually leading to grain polymerization; after adsorption, the surface of the sample no longer has obvious uniform pore structure, and the phenomenon of grain aggregation is obvious as that of the acid-washed sample, so that the sample is proved to not cause any new structural change when lithium is adsorbed.
Claims (7)
1. The preparation method of the bentonite modified metatitanic acid type lithium ion sieve precursor is characterized by comprising the following steps of:
(1) Respectively adding Ti (SO) 4 ) 2 And C 2 H 7 LiO 4 Dissolving to obtain Ti (SO) 4 ) 2 Solution and C 2 H 7 LiO 4 A solution;
(2) To Ti (SO) 4 ) 2 Adding precipitant dropwise into the solution to obtain white TiO (OH) 2 Precipitation, then adding TiO (OH) 2 Washing the precipitate with deionized water until no SO exists 4 2- Residue;
(3) TiO (OH) after washing in the step (2) 2 Diluting the precipitate with water, pulping, and dripping C in step (1) into the slurry 2 H 7 LiO 4 After the solutions are uniformly mixed, dropwise adding a complexing agent into the mixed solution, and stirring to obtain transparent yellow sol after the dropwise adding is completed;
(4) Adding bentonite into the transparent yellow sol obtained in the step (3), wherein the solid-to-liquid ratio of the bentonite to the transparent yellow sol is 1g:0.5-0.7L, stirring for 2-4h, aging for 10-14h, drying at 70-90 ℃ to obtain xerogel, grinding the xerogel, heating to 600-900 ℃ at the speed of 2-4 ℃/min, preserving heat for 1.5-3h, and calcining to obtain the transparent yellow sol.
2. The method for preparing bentonite-modified lithium-ion sieve precursor according to claim 1, wherein the precipitant in the step (2) is ammonia water, and the solution is dropwise added to a pH value of 7-9.
3. The method for preparing bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the complexing agent in the step (3) is a volume concentration25-35% H 2 O 2 。
4. The method for preparing bentonite-modified lithium meta-titanate precursor according to claim 3, wherein in step (3), H 2 O 2 The molar ratio of Ti to Ti in the mixed solution is 5-7:1.
5. The method for preparing a bentonite-modified meta-titanic acid type lithium ion sieve precursor according to claim 1, wherein the solid-to-liquid ratio of bentonite to transparent yellow sol in the step (4) is 1g:0.6L.
6. The method for preparing a bentonite-modified metatitanic acid type lithium ion sieve precursor according to claim 1, wherein the xerogel in the step (4) is ground and then heated to 750 ℃ at a speed of 3 ℃/min, and the temperature is kept for 2 hours.
7. A bentonite-modified metatitanic acid type lithium ion sieve precursor, characterized in that it is prepared by the method of any one of claims 1 to 6.
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