CN106622116B - A kind of preparation method of spinel-type lithium-ion sieve - Google Patents
A kind of preparation method of spinel-type lithium-ion sieve Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/18—Synthetic zeolitic molecular sieves
Abstract
A kind of preparation method of spinel-type lithium-ion sieve is related to a kind of preparation method for the inorganic adsorbent of adsorption recovery lithium from discarded automobile power cell positive electrode solution.Using lithium salts and manganese salt as raw material, and glycolic and tartaric acid are added as Compound-acid compounding agent, the ion sieve presoma Li of spinel-type is prepared using sol-gel method1.6Mn1.6O4.Acidleach is carried out to presoma with hydrochloric acid and obtains lithium ion sieve adsorbant, ion sieve selectivity and adsorption capacity are higher.It is an advantage of the invention that raw material are simple and easy to get, at low cost, preparation process is simple, and the adsorption capacity of ion sieve is high, low for equipment requirements, convenient for control.
Description
Technical field
The invention belongs to environmental resource circulation and stress technical fields, are related to a kind of preparation side of spinel-type lithium-ion sieve
Method, the ion sieve adsorbant is suitable for the adsorption recovery lithium from from discarded automobile power cell.
Background technique
Lithium is most light metal, has high electrode current potential and high electrochemical equivalent, and electrochemistry specific energy density is also suitable
Height, meanwhile, lithium due to receiving height to the superior storge quality of electric energy and the important value in nuclear energy uses in recent years
To pay attention to, the battery of big electricity capacity, the demand of the industry products such as aluminium lithium alloy articles and cellular li-ion battery are greatly improved,
The lithium consumption of China is promoted linearly to increase every year.Wherein, electric car (electric vehicle, EV) and mixing electricity
The a large amount of lithium resource of demand in core power battery in electrical automobile (hybrid electric vehicle, HEV).Electricity
The booming center of electrical automobile is in China, it is contemplated that by 2018, the demand of electric car was probably 4,700,000, battery
Demand is about 200GWh.In fact, arriving the year two thousand twenty according to national planning, China's electric car ownership will reach 5,000,000
, on entire industry chain (supply chain), battery is the most key link, accounts for the 40%~60% of integral vehicle cost.And in recent years, lithium
The demand of resource is every to be increased every year with 10% speed.It can be seen that making with the rapid growth of domestic ev industry
Also become very powerful and exceedingly arrogant for the lithium resource of electric car and hybrid-electric car critical material.And in discarded power battery,
Containing a large amount of lithium resource, recycling and reusing is carried out to these lithium resources, existing resource can be made full use of, plays green warp
Ji.
Ion-sieve type oxide is also referred to as ion sieve, is a kind of inorganic compound with gap structure, first by purpose
Ion and a kind of inorganic matter generate corresponding composite oxides through series reaction, and this oxide is referred to as ion sieve forerunner
Body extracts purpose ion therefrom then under the premise of not destroying presoma crystal structure to get corresponding ion is arrived
Sieve.Gap in ion sieve crystal structure is to the former ability for importing purpose ion and having screening and memory, i.e. ion sieve effect.Cause
This, under the case where different kinds of ions exists jointly, the property of can choose ground separation and Extraction purpose ion.Rich lithium lithium manganese oxide is most
It is early applied by Japanese scholars in lithium ion sieve field.This kind of lithium manganese oxide is equivalent in LiMn2O4Li is mixed in lattice+, make
Mn therein all becomes Mn4+, to avoid the molten damage of Mn during acidleach, improve the stability of spinel structure.This
Outside, such lithium manganese oxide does not introduce other metal ions, and spinel crystal lattice will not deformation occurs, does not influence Li+Freedom
It enters and leaves.Therefore, the drawbacks of rich lithium lithium manganese oxide can overcome doped lithium manganese oxide, before becoming lithium ion sieve field most
The material of scape.
Li1.6Mn1.6O4Lithium manganese the mass ratio of the material reaches 1, and theory lithium content with higher is higher than traditional spinelle
LiMn2O4And Li1.33Mn1.67O4.Presoma Li1.6Mn1.6O4Through lithium ion sieve MnO made from overpickling4·0.5H2O is considered as
At present to the maximum lithium ion adsorbent of lithium adsorption capacity.So studying the lithium ion sieve presoma haveing excellent performance
Li1.6Mn1.6O4And its ion sieve, it has an important significance for recycling lithium from the resources such as waste battery, it can also be very big
Urgent need of the alleviation world market of degree for lithium salts.The synthetic method of lithium manganese oxide mainly include high-temperature sintering process,
Microwave sintering method, the precipitation method, hydro-thermal method and sol-gal process.Sol-gal process is used in this method, the advantage is that sintering temperature
Spend lower, product particle size uniform form is regular, and crystal phase is purer etc..
In order to obtain the excellent lithium ion sieve of absorption property, while extending the service life of lithium ion sieve, can add multiple
It closes acid and is used as compounding agent, while lithium ion sieve presoma is prepared using sol-gel method, the ion sieve selection that the method is prepared
Property it is high, while to Li+Saturation exchange capacity it is higher, and the molten loss rate of manganese ion can be reduced.Use Compound-acid as cooperation
Agent, due to the increase of carboxyl and hydroxy functional group, so that raw material reaction is more abundant, produces in the reaction process of lithium source and manganese source
Object structure is more stable, to can make the molten loss rate of lithium higher during acidleach, the molten loss rate of manganese is lower.Therefore, it prepares
The ion sieve pattern come is uniform and possesses higher adsorption capacity.
Summary of the invention
The purpose of the present invention is to provide a kind of steady chemical structure, the system of the good lithium ion sieve adsorbant of absorption property
Preparation Method adds glycolic and tartaric acid as Compound-acid compounding agent, synthesizes rich lithium lithium manganese oxidation using the method for sol-gel
Object carries out acid de- lithium to it as presoma, obtains the lithium ion sieve of function admirable.
A kind of preparation method of spinel-type lithium-ion sieve, which is characterized in that
It (1) is raw material with lithium salts and manganese salt, it is soluble in water to be uniformly mixed；
(2) Compound-acid compounding agent is weighed, and is substantially soluble in water；The lithium manganese solution that step (1) obtains is added dropwise to compound
In acid cooperation agent solution, it is allowed to be sufficiently mixed；Compound-acid compounding agent is glycolic and tartaric acid；
(3) mixed solution for obtaining step (2) 75 DEG C~85 DEG C 6~8h of water bath processing under conditions of being stirred continuously,
Obtain gelatinous precipitate；
(4) precipitating obtained by step (3) is placed in 1~2h of drying in 150 DEG C of baking ovens, and be fully ground in the agate mortar
It is even, solid powder is obtained, powder is roasted into 5h~7h under conditions of 500 DEG C~600 DEG C, obtains ion sieve presoma
Li1.6Mn1.6O4。
(5) the ion sieve presoma Li for obtaining step (4)1.6Mn1.6O4Powder carries out acidleach processing with hydrochloric acid solution, most
After obtain ion sieve adsorbant.
Further, lithium salts is lithium carbonate, lithium nitrate or lithium acetate, and manganese salt is manganese carbonate, manganese nitrate or manganese acetate.
Further, the mol ratio of (lithium acetate+manganese acetate)/(glycolic+tartaric acid) is 1:1, wherein glycolic and wine
The mol ratio of stone acid is 3:1~1:1.
Further, lithium manganese solution is added dropwise to the speed in Compound-acid compounding agent is 10~15 ml/mins.
Further, Li/Mn molar ratio is 1:1.
Advantages of the present invention and have the active effect that preparation process is simple, low raw-material cost, products therefrom is structural
Can be good, Selective adsorption is high, can carry out effective adsorption recovery to the lithium in abandoned car power battery anode material, have
Help environmentally protective, resources circulation recycling.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of ion sieve adsorbant and its presoma
Fig. 2 is that the SEM of 1 gained ion sieve presoma of embodiment schemes, and Fig. 3 is that the SEM of ion sieve adsorbant schemes
Fig. 4 is the XRD diagram of 1 gained ion sieve presoma of embodiment and ion sieve adsorbant
Fig. 5 is Li emigration and Mn molten loss rate curve graph of the ion sieve presoma in acid solution
Specific embodiment
Below using lithium acetate, manganese acetate and lithium carbonate, manganese carbonate as raw material, the embodiment of the present invention is retouched in detail
It states.
Embodiment 1:
(1) lithium acetate (CH is weighed3COOLi·2H2O) 4.41g, manganese acetate (C4H6MnO4·4H2O) 10.59g is soluble in water
It is uniformly mixed；
(2) weigh glycolic 6.57g, tartaric acid 4.32g mixing is soluble in water, by lithium acetate, manganese acetate mixed solution with
The speed of 10 ml/mins is added dropwise in Compound-acid cooperation agent solution, and stirring is allowed to adequately mix；
(3) mixed solution in step (2) is placed in water-bath and is stirred continuously lower water-bath 8h for 75 DEG C, obtain pale pink glue
Shape precipitating；
(4) gelatinous precipitate substance is put in 150 DEG C of baking ovens dry 2h, obtains fluffy solid, grinds in the agate mortar
It is put into Muffle furnace after claying into power with 500 DEG C of heat preservation 7h, obtains ion sieve presoma Li1.6Mn1.6O4；
(5) 0.1gLLi is taken1.6Mn1.6O4Powder is put into 100mL, and acidleach is for 24 hours, flat to acidleach in the HCl solution of 0.5mol/L
After weighing apparatus, filtration drying obtains ion sieve adsorbant.
The XRD of presoma is shown in Fig. 4 that SEM is shown in Fig. 2；The XRD of ion sieve is shown in Fig. 4 that SEM is shown in Fig. 3；Before ion sieve
Driving body, the molten loss rate curve of the emigration of lithium and manganese is shown in Fig. 5 when acidleach in hydrochloric acid solution.As shown in Figure 4, knot before and after acidleach
Structure is almost the same, is still spinel structure, and only each characteristic diffraction peak is mobile to high angle direction, illustrates that interplanar distance d reduces,
This shows in acidleach process, Li+It is dissolved out from sample, leads to Lattice Contraction.By Fig. 2 and 3 it is found that acidleach is detached from front and back knot
It is little to be configured looks variation.As shown in Figure 5, ion sieve presoma is when acidleach reaches balance, the emigration of lithium and the molten loss rate of manganese
It is ideal.For obtained ion sieve in pH=12, lithium concentration is that equilibrium adsorption capacities are 35mg/ in the solution of 0.1mol/L
g。
Embodiment 2:
(1) lithium acetate (CH is weighed3COOLi·2H2O) 5.29g, manganese acetate (C4H6MnO4·4H2O) 12.71g is soluble in water
It is uniformly mixed；
(2) weigh glycolic 5.26g, tartaric acid 5.19g mixing is soluble in water, by lithium acetate, manganese acetate mixed solution with
The speed of 13 ml/mins is added dropwise in Compound-acid compounding agent acid solution, and stirring is allowed to adequately mix；
(3) mixed solution in step (2) is placed in water-bath and is stirred continuously lower water-bath 7h for 80 DEG C, obtain pale pink glue
Shape precipitating；
(4) gelatinous precipitate substance is put in 150 DEG C of baking ovens dry 1h, obtains fluffy solid, grinds in the agate mortar
It is put into Muffle furnace after claying into power with 550 DEG C of heat preservation 6h, obtains ion sieve presoma Li1.6Mn1.6O4；
(5) 0.1gLLi is taken1.6Mn1.6O4Powder is put into 100mL, and acidleach is for 24 hours, flat to acidleach in the HCl solution of 0.5mol/L
After weighing apparatus, filtration drying obtains ion sieve adsorbant.
The XRD diagram of ion sieve and its presoma, SEM figure and the molten damage curve graph of acidleach are similar in embodiment 1；Before acidleach
Significant change does not occur for structure afterwards, is spinel structure, and pattern variation is smaller before and after acidleach.Ion sieve in pH=12,
Lithium concentration is that equilibrium adsorption capacities are 36mg/g in the solution of 0.1mol/L.
Embodiment 3:
(1) lithium acetate (CH is weighed3COOLi·2H2O) 5.87g, manganese acetate (C4H6MnO4·4H2O) 14.12g is soluble in water
It is uniformly mixed；
(2) weigh glycolic 3.29g, tartaric acid 6.49g mixing is soluble in water, by lithium acetate, manganese acetate mixed solution with
The speed of 15 ml/mins is added dropwise in Compound-acid cooperation agent solution, and stirring is allowed to adequately mix；
(3) mixed solution in step (2) is placed in water-bath and is stirred continuously lower water-bath 6h for 85 DEG C, obtain pale pink glue
Shape precipitating；
(4) gelatinous precipitate substance is put in 150 DEG C of baking ovens dry 1h, obtains fluffy solid, grinds in the agate mortar
It is put into Muffle furnace after claying into power with 600 DEG C of heat preservation 5h, obtains ion sieve presoma Li1.6Mn1.6O4；
(5) 0.1gLLi is taken1.6Mn1.6O4Powder is put into 100mL, and acidleach is for 24 hours, flat to acidleach in the HCl solution of 0.5mol/L
After weighing apparatus, filtration drying obtains ion sieve adsorbant.
The XRD diagram of ion sieve and its presoma, SEM figure and the molten damage curve graph of acidleach are similar in embodiment 1；Before acidleach
Significant change does not occur for structure afterwards, is spinel structure, and pattern variation is smaller before and after acidleach.Ion sieve in pH=12,
Lithium concentration is that equilibrium adsorption capacities are 38mg/g in the solution of 0.1mol/L.
Embodiment 4:
(1) lithium carbonate (Li is weighed2CO3) 4.86g, manganese carbonate (MnCO3) 15.14g it is soluble in water be uniformly mixed；
(2) weigh glycolic 7.51g, tartaric acid 14.82g mixing is soluble in water, by lithium carbonate, manganese carbonate mixed solution with
The speed of 15 ml/mins is added dropwise in Compound-acid cooperation agent solution, and stirring is allowed to adequately mix；
(3) mixed solution in step (2) is placed in water-bath and is stirred continuously lower water-bath 6h for 85 DEG C, it is gluey heavy to obtain
It forms sediment；
(4) gelatinous precipitate substance is put in 150 DEG C of baking ovens dry 1h, obtains fluffy solid, grinds in the agate mortar
It is put into Muffle furnace after claying into power with 600 DEG C of heat preservation 5h, obtains ion sieve presoma Li1.6Mn1.6O4；
(5) 0.1gLLi is taken1.6Mn1.6O4Powder is put into 100mL, and acidleach is for 24 hours, flat to acidleach in the HCl solution of 0.5mol/L
After weighing apparatus, filtration drying obtains ion sieve adsorbant.
The XRD diagram of ion sieve and its presoma, SEM figure and the molten damage curve graph of acidleach are similar in embodiment 1；Before acidleach
Significant change does not occur for structure afterwards, is spinel structure, and pattern variation is smaller before and after acidleach.Ion sieve in pH=12,
Lithium concentration is that equilibrium adsorption capacities are 36mg/g in the solution of 0.1mol/L.
In above embodiments during acidleach the molten loss rate of manganese 5% hereinafter, the emigration of lithium is 96% or more.
Claims (5)
1. a kind of preparation method of spinel-type lithium-ion sieve, which is characterized in that
It (1) is raw material with lithium salts and manganese salt, it is soluble in water to be uniformly mixed；
(2) Compound-acid compounding agent is weighed, and is substantially soluble in water；The lithium manganese solution that step (1) obtains is added dropwise to Compound-acid to match
In mixture solution, it is allowed to be sufficiently mixed；Compound-acid compounding agent is glycolic and tartaric acid；
(3) mixed solution for obtaining step (2) 75 DEG C~85 DEG C 6~8h of water bath processing under conditions of being stirred continuously, obtain
Gelatinous precipitate；
(4) precipitating obtained by step (3) is placed in 1~2h of drying in 150 DEG C of baking ovens, and is fully ground in the agate mortar uniformly,
Solid powder is obtained, powder is roasted into 5h~7h under conditions of 500 DEG C~600 DEG C, obtains ion sieve presoma
Li1.6Mn1.6O4；
(5) the ion sieve presoma Li for obtaining step (4)1.6Mn1.6O4Powder carries out acidleach processing with hydrochloric acid solution, finally
To ion sieve adsorbant.
2. manganese salt is carbon the method according to claim 1, wherein lithium salts is lithium carbonate, lithium nitrate or lithium acetate
Sour manganese, manganese nitrate or manganese acetate.
3. according to the method described in claim 2, it is characterized in that, (lithium acetate+manganese acetate)/(glycolic+tartaric acid) rubs
Your proportion is 1:1, and wherein the mol ratio of glycolic and tartaric acid is 3:1~1:1.
4. the method according to claim 1, wherein lithium manganese solution is added dropwise to the speed in Compound-acid compounding agent
For 10~15 ml/mins.
5. the method according to claim 1, wherein Li/Mn molar ratio is 1:1.
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| CN107138126A (en) * | 2017-07-18 | 2017-09-08 | 河北工程大学 | A kind of preparation method of lithium ion sieve adsorbant and the method for adsorbing lithium ion |
| CN112342378A (en) * | 2018-03-31 | 2021-02-09 | 南京霄祥工程技术有限公司 | Lithium ion adsorbent and preparation method thereof |
| CN109012600A (en) * | 2018-09-17 | 2018-12-18 | 天津市职业大学 | A kind of activated carbon supported lithium ion sieve filler and its methods for making and using same |
| CN109289758B (en) * | 2018-12-07 | 2021-04-02 | 中国科学院青海盐湖研究所 | Hexagonal flaky manganese lithium ion sieve adsorbent and preparation method thereof |
| CN109289757B (en) * | 2018-12-07 | 2021-03-16 | 中国科学院青海盐湖研究所 | Hexagonal dendritic manganese lithium ion sieve adsorbent and preparation method thereof |
| CN110028104A (en) * | 2019-03-28 | 2019-07-19 | 长沙师范学院 | A kind of preparation method of compound manganese lithium system ion sieve |
| CN110479228A (en) * | 2019-08-16 | 2019-11-22 | 黄冈师范学院 | A kind of regeneration method of the ion-sieve type manganese systems adsorbent of failure |
| CN110898794B (en) * | 2019-12-13 | 2023-02-07 | 中国科学院青海盐湖研究所 | Preparation method of lithium ion sieve |
| CN113292102A (en) * | 2021-05-25 | 2021-08-24 | 福建省云智新材料科技有限公司 | Preparation method of single crystal lithium manganese oxide for lithium ion sieve |
| CN113856490A (en) * | 2021-10-11 | 2021-12-31 | 中南大学 | Preparation method of lithium ion sieve membrane and two-stage electrodialysis device |
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| CN101961634A (en) * | 2010-09-16 | 2011-02-02 | 中南大学 | Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof |
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