CN103991908B - By the method for cation doping regulation and control lithium ion sieve stability - Google Patents

By the method for cation doping regulation and control lithium ion sieve stability Download PDF

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CN103991908B
CN103991908B CN201410192796.5A CN201410192796A CN103991908B CN 103991908 B CN103991908 B CN 103991908B CN 201410192796 A CN201410192796 A CN 201410192796A CN 103991908 B CN103991908 B CN 103991908B
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lithium
ion
manganese
sieve
composite oxides
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CN103991908A (en
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孙淑英
肖伽励
聂骁垚
曹伟
蔡丽娟
宋兴福
于建国
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East China University of Science and Technology
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Abstract

The invention discloses a kind of method by cation doping regulation and control lithium ion sieve stability, comprise and prepare composite oxides Li 4mn xr yo 12wherein dopant ion R is Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5, described preparation comprises: (1) is by manganous salt, lithium salts and contain R compound, make dopant ion R/ manganese/lithium mol ratio for (0.625 ~ 0.001): (0.625 ~ 1.249): 1.00, and (R+ manganese)/lithium mol ratio is 1.1 ~ 1.5; (2) mixture that step (1) obtains is calcined 6 ~ 120h under 350 ~ 650 DEG C of dynamic air conditions, obtain described composite oxides.One is also provided to prepare ion(ic)sieve Mn x/5r y/5o 20.31H 2the method of O, by composite oxides washing, drying, then through leaching de-agent leaching Li +.Present invention process route is simple, and preparation condition is gentle, and reaction time is short, and the Emission in Cubic ion(ic)sieve of acquisition has stable structure and higher adsorptive capacity.

Description

By the method for cation doping regulation and control lithium ion sieve stability
Technical field
The present invention relates to a kind of method by cation doping regulation and control lithium ion sieve stability, be specifically related to one and prepare Li 4mn xr yo 12composite oxides (wherein R=Sn, Zr, Ti, Fe, Ni, Co or Al) and manganese system ion(ic)sieve sorbent material Mn x/5r y/5o 20.31H 2the method of O.
Background technology
The special physico-chemical property of lithium is widely applied to many fields.From salt lake or seawater, effectively extract lithium is the important aspect solving world today's lithium breach.
China is a resource big country, and liquid lithium resource is very abundant.But low grade brine or seawater are the principal modes that China's liquid lithium resource exists.From salt lake brine, the method for extraction and isolation lithium mainly contains the precipitator method, solvent extration.But these traditional separating and extracting method are not suitable for carrying lithium from low grade brine or seawater, the bittern that especially Mg/Li ratio is very high.And the angle from environment or the angle from economy consider that absorption method all has larger advantage than additive method, especially more obvious in the advantage carrying lithium from low grade brine or seawater.The key of absorption method develops the sorbent material of excellent property, and it requires that sorbent material has high selectivity to lithium, to eliminate the interference of a large amount of coexisting ion in bittern.Spinel type Manganse Dioxide has unique three-dimensional internal tunnel, is beneficial to Li +embedding with deviate from, be thus widely used as electrode materials and the sorbent material of lithium cell.
MnO 20.31H 2o is a kind of manganese bioxide ionic sieve that search time is longer, adsorptive capacity is higher, performance is comparatively stable.
By Emission in Cubic Li 4mn 5o 12the MnO that composite oxides pickling obtains 20.31H 2o ion(ic)sieve is because preparation method is relatively simple and have larger lithium ion adsorptive capacity and less mn ion and sieve molten damage amount and obtain in lithium ion sieve field and study widely.Although this ion(ic)sieve only should have Mn in theory 4+, the molten damage situation of manganese should do not had to occur.But in actual fabrication process owing to being difficult to whole manganese to be oxidized to tetravalence, cause the generation still cannot avoiding the molten damage of manganese in acid cleaning process.
Summary of the invention
The invention provides a kind of simple toward Emission in Cubic Li 4mn 5o 12the method of middle doped metal ion, mainly utilizes and has the metal ion of the tetravalence of more strong bond or valence state to adulterate lower than the metal of tetravalence with oxygen, thus stable crystal structure or improve manganese valence thus reduce the molten damage amount of manganese of acid process.Meanwhile, the impact of research doping on lithium ion adsorptive capacity.
Method by cation doping regulation and control lithium ion sieve stability of the present invention, comprises and prepares lithium ion sieve precursor composite oxides Li 4mn xr yo 12, wherein dopant ion R be Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0, described composite oxides Li 4mn xr yo 12preparation comprise: (1) is by manganous salt, lithium salts and containing the compound of R, make dopant ion R/ manganese/lithium mol ratio for (0.625 ~ 0.001): (0.625 ~ 1.249): 1.00, and (R+ manganese)/Li mol ratio is 1.1 ~ 1.5; (2) mixture that step (1) obtains is calcined 6 ~ 120h under 350 ~ 650 DEG C of dynamic air conditions, obtain described composite oxides.
Method by cation doping regulation and control lithium ion sieve stability of the present invention, comprising: by composite oxides Li of the present invention 4mn xr yo 12washing, drying, then leach Li through the de-agent of leaching, obtain the lithium ion sieve Mn of described cation doping x/5r y/5o 20.31H 2o.
The present invention also provides a kind of composite oxides Li 4mn xr yo 12, wherein dopant ion R be Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0.
The present invention also provides a kind of cation doping lithium ion sieve Mn x/5r y/5o 20.31H 2o, wherein dopant ion R be Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0.
Compared with prior art, the present invention has following beneficial effect:
1, cheaper starting materials is easy to get, the elemental lithium of use and the mol ratio of manganese element lower, few containing lithium wastage of material;
2, the calcining temperature used is lower, can to 350 DEG C, and calcination time is the shortest can to 6h, and the product component obtained is single, epigranular;
3, synthetic method of the present invention, experiment condition, product proportioning easily control, and the condition and range that can obtain desired product is wide; And
4, the Emission in Cubic Li of the present invention's synthesis 4mn xr yo 12, it has spinel structure, stable in properties; Synthesize the ion(ic)sieve Mn obtained x/5r y/5o 20.31H 2o, has the molten damage of manganese and measures little lithium adsorptive capacity greatly, the advantage of good stability.It can be used for the lithium-containing solution such as salt lake brine, seawater and carries lithium.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the Emission in Cubic Li of the synthesis of example 1 4mn 4.75ti 0.25o 12xRD figure, wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ;
Fig. 2 is the Li that example 1 synthesizes 4mn 4.75ti 0.25o 12sEM figure;
Fig. 3 is the Li of the 2-in-1 one-tenth of example 4mn 4.5ti 0.5o 12xRD figure, wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ;
Fig. 4 is the ion(ic)sieve Mn that example 6 synthesizes 0.95ti 0.05o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ;
Fig. 5 is the ion(ic)sieve Mn that example 6 synthesizes 0.95ti 0.05o 20.31H 2the SEM figure of O;
Fig. 6 is the ion(ic)sieve Mn that example 7 synthesizes 0.98co 0.02o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ;
Fig. 7 is the ion(ic)sieve Mn that example 8 synthesizes 0.98al 0.02o 20.31H 2the SEM figure of O;
Fig. 8 is the ion(ic)sieve Mn that example 9 synthesizes 0.98ni 0.02o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is with the whole diffraction region Mn of the angle scanning of 2 θ 0.98ni 0.02o 20.31H 2o.
Embodiment
The object of the invention is to by past Emission in Cubic Li 4mn 5o 12in mix the positive quadrivalent metallic ion with oxygen with more high forces or valence state lower than four metal ion with obtain the more stable or manganese of structure closer to tetravalence Emission in Cubic Li 4mn xr yo 12and Mn x/5r y/5o 20.31H 2o ion(ic)sieve, thus reduce Li further 4mn 5o 12acid cleaning process manganese molten damage amount and improve the adsorptive capacity of corresponding ion(ic)sieve to lithium ion.The invention provides one and prepare Li 4mn xr yo 12(wherein R is Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5) and Mn x/5r y/5o 20.31H 2the simple method of O ion(ic)sieve.The compound that the present invention uses manganese salt cheap and easy to get, lithium salts and has a metal ion R obtains Emission in Cubic Li by low-temperature bake 4mn xr yo 12composite oxides; Then acid treatment is carried out to presoma, extract Li wherein, then obtain through washing, filtration, drying sorbent material lithium ion being had to screening effect; That is, the present invention uses better simply operational path to synthesize ion(ic)sieve sorbent material that is high with adsorptive capacity, good stability.Emission in Cubic Li of the present invention 4mn xr yo 12ternary compound oxides is suitable as the electrode materials of lithium cell.Ion(ic)sieve sorbent material Mn of the present invention x/5r y5o 20.31H 2o is particularly suitable for from containing enrichment extraction lithium lower concentration lithium high concentration impurities solution lithium-containing solutions such as (as:) salt lake brine, well water, seawater.
Prepare lithium ion sieve precursor composite oxides Li 4mn xr yo 12method, wherein dopant ion R be Sn, Zr, Ti, Fe, Ni, Co or Al, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0, comprise: (1), by manganous salt, lithium salts and the compound containing R, make dopant ion R/ manganese/lithium mol ratio for (0.625 ~ 0.001): (0.625 ~ 1.249): 1.00, and (R+ manganese)/Li mol ratio is 1.1 ~ 1.5; (2) mixture that step (1) obtains is calcined 6 ~ 120h under 350 ~ 650 DEG C of dynamic air conditions, obtain described composite oxides.
Preferably, described manganous salt is manganous carbonate, manganous sulfate, manganous fluoride, Manganous chloride tetrahydrate, manganese iodide or its combination.
Preferably, described lithium salts is lithium nitrate, Quilonum Retard, Lithium Sulphate, Trilithium phosphate, lithium hydroxide, lithium chloride or its combination.
Preferably, the described compound containing R is tindioxide, zirconium dioxide, zirconium sulfate, zirconium chloride, zirconium nitrate, titanium dioxide, titanium sulfate, tetrabutyl titanate, iron nitrate, ironic hydroxide, ferric sulfate, ferric oxide, iron(ic) chloride, nickel hydroxide, single nickel salt, nickelous nitrate, nickelous chloride, nickel oxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobaltous carbonate, cobaltous hydroxide, tricobalt tetroxide, aluminum nitrate, Tai-Ace S 150, aluminium hydroxide, aluminium sesquioxide or its combination.
Preferably, the mol ratio of R/ manganese/lithium is (0.01 ~ 0.16): (1.24 ~ 1.09): 1, described in be blended in water and carry out, and remove moisture before the calcining carrying out step (2).
Preferably, in step (1), the mol ratio of R/ manganese/lithium is (0.07 ~ 0.16): (1.17 ~ 1.09): 1, and in step (2), the temperature of calcining is 350 ~ 450 DEG C, and the time is 12 ~ 72h.
Lithium ion sieve Mn of the present invention x/5r y/5o 20.31H 2the preparation of O comprises described composite oxides Li 4mn xr yo 12washing, drying, then leach Li through the de-agent of leaching, obtain the lithium ion sieve Mn of described cation doping x/5r y/5o 20.31H 2o.
Preferably, described leaching takes off hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium persulphate that agent is 0.1 ~ 1mol/L.
Particularly, the present invention prepares Li 4mn xr yo 12composite oxides and manganese system ion(ic)sieve sorbent material Mn x/5r y/5o 20.31H 2the method of O comprises, and take R as titanium is example, following steps:
(1) by 4.2 × 10 -2~ 1.8mmol titanium sulfate and 14.2 ~ 12.1mmol Manganse Dioxide and 11.4mmol lithium nitrate mixed grinding even.Wherein, the mol ratio of titanium/manganese/lithium is made to be (0.01 ~ 0.16): (1.24 ~ 1.09): 1 (or using the tindioxide, zirconium dioxide, iron nitrate, nickelous nitrate, tricobalt tetroxide, aluminum nitrate etc. that can ensure above-mentioned R/ manganese/Li mol ratio to replace titanium sulfate);
(2), under the mixture that step (1) obtains being transferred to 350 ~ 450 DEG C of conditions (such as in retort furnace), in dynamic air, calcining 6 ~ 24h, obtain presoma;
(3) presoma step (2) obtained is after soaking de-agent leaching, dry, obtains ion(ic)sieve Mn x/5r y/5o 20.31H 2o.It is pointed out that the manganese salt that the present invention uses is not limited to above-mentioned Manganse Dioxide, can also be manganous carbonate, manganous sulfate, manganous fluoride, Manganous chloride tetrahydrate or manganese iodide; The lithium salts used is not limited to above-mentioned lithium nitrate, can also be lithium hydroxide, lithium nitrate, Quilonum Retard, Lithium Sulphate, Trilithium phosphate, lithium chloride; The zirconates used is not limited to above-mentioned zirconium dioxide, can also be zirconium sulfate, zirconium chloride, zirconium nitrate; The titanium salt used is not limited to above-mentioned titanium sulfate, can also be titanium dioxide, titanium sulfate, tetrabutyl titanate; The molysite used is not limited to above-mentioned iron nitrate, can also be ironic hydroxide, ferric sulfate, ferric oxide, iron(ic) chloride; The nickel salt used is not limited to above-mentioned nickelous nitrate, can also be nickel hydroxide, single nickel salt, nickelous chloride, nickel oxide; The cobalt salt used is not limited to above-mentioned cobalt dioxide, can also be Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobaltous carbonate, cobaltous hydroxide; The aluminium salt used is not limited to above-mentioned aluminum nitrate, can also be Tai-Ace S 150, aluminium hydroxide, aluminium sesquioxide; Above-mentioned leaching takes off hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium sulphite that agent is 0.1 ~ 1mol/L.The preferred technical solution of the present invention is: in preferred steps (1), the mol ratio of tetravalence R, bivalent manganese and monovalence lithium is (0.07 ~ 0.16): (1.17 ~ 1.09): 1, in preferred steps (2), the temperature of calcining is 350 ~ 450 DEG C, and the time is 12 ~ 24h.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
example 1
11.4mmol lithium nitrate is dissolved in 15ml deionized water, then adds 14.2mmol Manganse Dioxide and 4.2 × 10 -2mmol titanium sulfate, 80 DEG C of stirred in water bath, removes completely to water; The mixture obtained is transferred in retort furnace, calcines 24 hours under 350 DEG C of conditions, obtain presoma Li 4mn 4.75ti 0.25o 12, the XRD figure of this product is shown in Fig. 1, and SEM figure is shown in Fig. 2; From Fig. 1,2, the Li of pure phase can be obtained under adopted calcination condition 4mn 4.75ti 0.25o 12, and product particle size is more even.Get 0.8g presoma and be placed in 200ml0.5mol/L hydrochloric acid soln, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material Mn of the present invention 0.95ti 0.05o 20.31H 2o.
example 2
1.0mmol ironic hydroxide and 90.0mmol lithium nitrate and 99.0mmol manganous carbonate mixed grinding are evenly placed in retort furnace, calcine 24 hours under 400 DEG C of conditions, wherein air velocity is 50mL/min, obtains Li 4mn 4.5fe 0.5o 12, the XRD figure of this product is shown in Fig. 3.Get 0.8g presoma and be placed in 200ml0.5mol/L hydrochloric acid soln, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material Mn of the present invention 0.9fe 0.1o 20.31H 2o.The molten damage of this acid cleaning process manganese is 0.7%.
example 3
39.9mmol lithium chloride is dissolved in 20ml deionized water, then adds 1.0mmol zirconium dioxide and 44.8mmol manganous sulfate, 80 DEG C of stirred in water bath, to the complete evaporate to dryness of water; The mixture obtained is transferred in retort furnace, calcines 48 hours with under 450 DEG C of conditions, obtain presoma Li 4mn 4zrO 12.Get 0.8g presoma and be placed in 200ml0.5mol/L ammonium persulfate solution, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material Mn of the present invention 0.8zr 0.2o 20.31H 2o.The molten damage of this acid cleaning process manganese is 0.5%.
example 4
39.9mmol lithium chloride is dissolved in 20ml deionized water, then adds 1.0mmol tindioxide and 44.8mmol manganous sulfate, 80 DEG C of stirred in water bath, to the complete evaporate to dryness of water; The mixture obtained is transferred in retort furnace, calcines 48 hours with under 450 DEG C of conditions, obtain presoma Li 4mn 4snO 12.Get 0.8g presoma and be placed in 200ml0.5mol/L ammonium persulfate solution, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material Mn of the present invention 0.8sn 0.2o 20.31H 2o.The molten damage of this acid cleaning process manganese is 0.6%.
example 5
Get the presoma 0.8gLi of example 1 4mn 4.75ti 0.25o 12add 200mL0.5mol/L ammonium persulfate solution, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material Mn of the present invention 0.95ti 0.05o 20.31H 2o.The molten damage of this acid cleaning process manganese is 0.7%.
example 6
Get the 0.8gLi of example 1 4mn 4.75ti 0.25o 12add 200mL0.1mol/LHCl solution, put into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching +; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings -5Ω -1m -1for standard, suction filtration, dry 8h in 120 DEG C of still airs, namely obtain ion(ic)sieve Mn of the present invention 0.95ti 0.05o 20.31H 2o.This ion(ic)sieve XRD figure is shown in Fig. 4, and this ion(ic)sieve SEM figure is shown in Fig. 5; Fig. 1 and Fig. 4 contrast can be found, before and after pickling, structure there is no obvious change, is still spinel structure.Contrasted by Fig. 2 and Fig. 5 known, after pickling not there is considerable change in ion(ic)sieve pattern.
example 7
80.0mmol lithium nitrate is dissolved in 20ml deionized water, then adds 98.0mmol manganous carbonate and 1.0mmol cobalt sesquioxide adds.Be placed in 80 DEG C of stirred in water bath, evaporation drying.Transfer in retort furnace by the mixture obtained, calcine 24 hours under 450 DEG C of conditions, after cooling, in 1mol/l ammonium persulfate solution, wash-out obtains ion(ic)sieve Mn 0.98co 0.02o 20.31H 2o.The molten loss rate of acid cleaning process manganese is only 0.7%.The XRD figure of this product is shown in 6.
example 8
40mmol lithium hydroxide is dissolved in 5ml deionized water, then adds 49mmol Manganous chloride tetrahydrate and 1mmol aluminum nitrate, be placed on 80 DEG C of stirred in water bath, evaporation drying.In mortar, grinding evenly; Transfer in retort furnace by the mixture obtained, calcine 24 hours under 400 DEG C of conditions, after cooling, in 1mol/l hydrochloric acid soln, wash-out obtains ion(ic)sieve Mn 0.98al 0.02o 20.31H 2o.The molten loss rate of acid cleaning process manganese is only 0.9%.The SEM figure of this product is shown in Fig. 7.
example 9
80.0mmol lithium nitrate is dissolved in 20ml deionized water, then adds 98.0mmol manganous carbonate and 2.0mmol single nickel salt adds.Be placed in 80 DEG C of stirred in water bath, evaporation drying.Transfer in retort furnace by the mixture obtained, calcine 24 hours under 450 DEG C of conditions, after cooling, in 1mol/l ammonium persulfate solution, wash-out obtains ion(ic)sieve Mn 0.98ni 0.02o 20.31H 2o.The molten loss rate of acid cleaning process manganese is only 1%.The XRD figure of this product is shown in Fig. 8.
adsorption effect test 1
The sample ions sieve adsorbant (respectively Doped with Titanium, iron, zirconium, cobalt, al and ni ion) taken respectively prepared by 100mg example 1,2,3,7,8 and 9 puts into tool sieve Erlenmeyer flask, adds 10mL10mmol/L mixed ion solutions (Li +, Na +, K +, Ca 2+, and Mg 2+, pH=10.1), be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, reaction 120h, gets the concentration that supernatant IC monitors wherein each ion, the results are shown in Table 1.
The adsorption selectivity of table 1 ion(ic)sieve
As shown in Table 1, this ion(ic)sieve has higher selectivity to the absorption of Li ion compared with common coexisting ion, carries lithium and Extracting Lithium from Seawater has important practical value to salt lake.
adsorption effect test 2
The sample ions sieve taken respectively prepared by 100mg example 1,3 and 6 puts into tool sieve Erlenmeyer flask, adds 100mL Cha Er Han bittern.Be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, reaction 48h, get the concentration that supernatant IC monitors wherein lithium ion, the amount of the absorption lithium ion of ion(ic)sieve is respectively 3.2mmol/g, 5.5mmol/g and 4.1mmol/g.
Comparison test:
Take the MnO of 100mg example 4 and other ions that undope respectively 20.4H 2sample ions sieve prepared by O puts into tool sieve Erlenmeyer flask, adds 100mL Cha Er Han bittern.Be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, and reaction 48h, get the concentration that supernatant IC monitors wherein lithium ion, the amount of the absorption lithium ion of ion(ic)sieve is respectively 3.8mmol/g and 3.5mmol/g.The molten loss rate of manganese is 0.4% and 2% respectively.This shows by selecting suitable dopant ion and doping effectively can not only improve the adsorptive capacity of ion(ic)sieve to lithium ion, and significantly reduce the molten loss rate of manganese, prepared the product that stability is more excellent.
It will be appreciated by those skilled in the art that the improvement of stability is mainly embodied in the reduction of the molten loss rate of manganese.The molten loss rate of manganese reduces, and ion(ic)sieve just can use more time, that is improves stability.
From the various embodiments described above, synthetic method of the present invention, experiment condition, product proportioning easily control, and the condition and range that can obtain desired product is wide; The present invention synthesizes the ion(ic)sieve sorbent material Mn obtained x/5r y/5o 20.31H 2o (wherein R=Sn, Zr, Ti, Fe, Ni, Co or Al) its can be used for the lithium-containing solution such as salt lake brine, seawater and carry lithium, and it is large to have adsorptive capacity, reproducible advantage.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.

Claims (10)

1., by a method for cation doping regulation and control lithium ion sieve stability, comprise and prepare lithium ion sieve precursor composite oxides Li 4mn xr yo 12, wherein dopant ion R is Sn or Zr, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0, described composite oxides Li 4mn xr yo 12preparation comprise:
(1) by manganous salt, lithium salts and the compound containing R, make the mol ratio of R/ manganese/lithium for (0.625 ~ 0.001): (0.625 ~ 1.249): 1.00, and (R+ manganese)/lithium mol ratio is 1.1 ~ 1.5;
(2) mixture that step (1) obtains is calcined 6h ~ 120h under 350 DEG C ~ 650 DEG C dynamic air conditions, obtain described composite oxides.
2. method according to claim 1, is characterized in that, in step (1), described manganous salt is manganous carbonate, manganous sulfate, manganous fluoride, Manganous chloride tetrahydrate, manganese iodide or its combination.
3. method according to claim 1, is characterized in that, in step (1), described lithium salts is lithium nitrate, Quilonum Retard, Lithium Sulphate, Trilithium phosphate, lithium chloride or its combination.
4. method according to claim 1, is characterized in that, in step (1), R is Sn, and the described compound containing R is tindioxide; R is Zr, and the described compound containing R is zirconium dioxide, zirconium sulfate, zirconium chloride, zirconium nitrate or its combination.
5. method according to claim 1, it is characterized in that, in step (1), the mol ratio of R/ manganese/lithium is (0.01 ~ 0.16): (1.24 ~ 1.09): 1, described being blended in water is carried out, and removes moisture before the calcining carrying out step (2).
6. method according to claim 1, it is characterized in that, in step (1), the mol ratio of R/ manganese/lithium is (0.07 ~ 0.16): (1.17 ~ 1.09): 1, and the temperature of calcining is 350 DEG C ~ 450 DEG C in step (2), the time is 12h ~ 72h.
7., by a method for cation doping regulation and control lithium ion sieve stability, comprising: by the composite oxides Li obtained in any one of claim 1-6 4mn xr yo 12washing, drying, then leach Li through the de-agent of leaching, obtain the lithium ion sieve Mn of described cation doping x/5r y/5o 20.31H 2o.
8. method as claimed in claim 7, it is characterized in that, described leaching takes off hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium persulphate that agent is 0.1mol/L ~ 1.0mol/L.
9. a composite oxides Li 4mn xr yo 12, wherein dopant ion R is Sn or Zr, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0.
10. a cation doping lithium ion sieve Mn x/5r y/5o 20.31H 2o, wherein dopant ion R is Sn or Zr, and 2.5≤x≤4.996,0.004≤y≤2.5, x+y is 5.0.
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