CN103991908A - Method for regulating and controlling stability of lithium ion sieve by cation doping - Google Patents

Method for regulating and controlling stability of lithium ion sieve by cation doping Download PDF

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CN103991908A
CN103991908A CN201410192796.5A CN201410192796A CN103991908A CN 103991908 A CN103991908 A CN 103991908A CN 201410192796 A CN201410192796 A CN 201410192796A CN 103991908 A CN103991908 A CN 103991908A
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lithium
manganese
ion
sieve
nitrate
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CN103991908B (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 method for regulating and controlling stability of a lithium ion sieve by cation doping. Preparation of a composite oxide Li4MnxRyO12 is included, wherein doped ion R is Sn, Zr, Ti, Fe, Ni, Co or Al; x is greater than or equal to 2.5 and less than or equal to 4.996; y is greater than or equal to 0.004 and less than or equal to 2.5; and x+y is 5. The preparation method comprises the following steps: (1) divalent manganese salt, lithium salt and an R-containing compound are mixed, molar ratio of doped ion R/manganese/lithium is (0.625-0.001): (0.625-1.249):1.00, and molar ratio of (R+manganese)/lithium is 1.1-1.5; and (2) the mixture obtained from the step (1) is calcined under the dynamic air condition of 350-650 DEG C for 6-120h so as to obtain the composite oxide. The invention also provides a method for preparing an ion sieve Mnx/5Ry/5O2.0.31H2O, comprising steps of: washing the composite oxide, drying and leaching with a leaching agent to obtain Li<+>.The method has advantages of simple process route, mild preparation condition and short reaction period. The obtained cubic phase ion sieve has a stable structure and high adsorption quantity.

Description

Regulate and control the method for lithium ion sieve stability by cation doping
Technical field
The present invention relates to a kind of method that regulates and controls lithium ion sieve stability by cation doping, 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 are 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.Effectively from salt lake or seawater, extracting lithium is the important aspect that solves 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.The method of extracting separating Li from salt lake brine 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 especially very high bittern of Mg/Li ratio.And consider that from the angle of environment or from economic angle absorption method all has larger advantage than additive method, especially more obvious in the advantage of carrying lithium from low grade brine or seawater.The key of absorption method is to develop the sorbent material of excellent property, and it requires sorbent material to have high selectivity to lithium, to eliminate the interference of a large amount of coexisting ions in bittern.Spinel type Manganse Dioxide has unique three-dimensional internal tunnel, is beneficial to Li +embedding with deviate from, thereby be 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 long, 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 compared with large lithium ion adsorptive capacity with compared with little mn ion and sieve molten damage amount and obtained research widely in lithium ion sieve field.Although this ion(ic)sieve only should have Mn in theory 4+, should not have the molten damage situation of manganese to occur.But owing to being difficult to that whole manganese is oxidized to tetravalence, cause still cannot avoiding the generation of the molten damage of manganese in actual fabrication process 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, is mainly to utilize with oxygen to have more metal ion or the valence state of the tetravalence of strong bond to adulterate lower than the metal of tetravalence, thereby thereby the valence state of stable crystal structure or raising manganese reduces the molten damage amount of manganese of acid process.Meanwhile, the impact of research doping on lithium ion adsorptive capacity.
The method that regulates and controls lithium ion sieve stability by cation doping 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 with 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 step (1) being obtained is calcined 6～120h under 350～650 DEG C of dynamic air conditions, obtains described composite oxides.
The method that regulates and controls lithium ion sieve stability by cation doping of the present invention, comprising: by composite oxides Li of the present invention 4mn xr yo 12washing, dry, then leach Li through soaking de-agent, 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, raw material is cheap and easy to get, and the elemental lithium of use and the mol ratio of manganese element are lower, few containing lithium wastage of material;
2, the calcining temperature using is lower, can be to 350 DEG C, and calcination time is the shortest can be to 6h, and the product component that obtains is single, epigranular;
3, synthetic method of the present invention, experiment condition, product proportioning are easily controlled, and the condition and range that can obtain desired product is wide; And
4, the synthetic Emission in Cubic Li of the present invention 4mn xr yo 12, it has spinel structure, stable in properties; The synthetic ion(ic)sieve Mn obtaining x/5r y/5o 20.31H 2o, having the molten damage of manganese, to measure little lithium adsorptive capacity large, the advantage of good stability.It can be used for the lithium-containing solution such as salt lake brine, seawater and carries lithium.
Brief description of the drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the synthetic Emission in Cubic Li of example 1 4mn 4.75ti 0.25o 12xRD figure, wherein, X-ray diffractometer is the whole diffraction region of angle scanning with 2 θ;
Fig. 2 is the synthetic Li of example 1 4mn 4.75ti 0.25o 12sEM figure;
Fig. 3 is the synthetic Li of example 2 4mn 4.5ti 0.5o 12xRD figure, wherein, X-ray diffractometer is the whole diffraction region of angle scanning with 2 θ;
Fig. 4 is the synthetic ion(ic)sieve Mn of example 6 0.95ti 0.05o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is the whole diffraction region of angle scanning with 2 θ;
Fig. 5 is the synthetic ion(ic)sieve Mn of example 6 0.95ti 0.05o 20.31H 2the SEM figure of O;
Fig. 6 is the synthetic ion(ic)sieve Mn of example 7 0.98co 0.02o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is the whole diffraction region of angle scanning with 2 θ;
Fig. 7 is the synthetic ion(ic)sieve Mn of example 8 0.98al 0.02o 20.31H 2the SEM figure of O;
Fig. 8 is the synthetic ion(ic)sieve Mn of example 9 0.98ni 0.02o 20.31H 2the XRD figure of O, wherein, X-ray diffractometer is the whole diffraction region Mn of angle scanning with 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 with oxygen have more pretend positive quadrivalent metallic ion firmly or valence state lower than four metal ion with obtain the more stable or manganese of structure more approach tetravalence Emission in Cubic Li 4mn xr yo 12and Mn x/5r y/5o 20.31H 2o ion(ic)sieve, thus Li further reduced 4mn 5o 12the molten damage amount of acid cleaning process manganese 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, lithium salts cheap and easy to get and has a metal ion R obtains Emission in Cubic Li by low-temperature bake 4mn xr yo 12composite oxides; Then presoma is carried out to acid treatment, extract Li wherein, then through washing, filtration, the dry sorbent material that obtains lithium ion to have screening effect; That is to say, the present invention uses better simply operational path to synthesize ion(ic)sieve sorbent material 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, makes 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 step (1) being obtained is calcined 6～120h under 350～650 DEG C of dynamic air conditions, obtains 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 of carrying out step (2).
Preferably, the mol ratio of R/ manganese/lithium be (0.07～0.16) in step (1): (1.17～1.09): 1, and the temperature of calcining in step (2) is 350～450 DEG C, 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, dry, then leach Li through soaking de-agent, obtain the lithium ion sieve Mn of described cation doping x/5r y/5o 20.31H 2o.
Preferably, described in, soak hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or ammonium persulphate that de-agent is 0.1～1mol/L.
Particularly, the present invention prepares Li 4mn xr yo 12composite oxides and manganese are ion(ic)sieve sorbent material Mn x/5r y/5o 20.31H 2the method of O comprises, take R as example as titanium, 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 are even.Wherein, the mol ratio that makes titanium/manganese/lithium is (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) mixture step (1) being obtained is transferred to (for example, in retort furnace) under 350～450 DEG C of conditions, calcines 6～24h in dynamic air, obtains presoma;
(3) presoma step (2) being obtained is through after soaking de-agent and soaking, 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 using 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 using is not limited to above-mentioned zirconium dioxide, can also be zirconium sulfate, zirconium chloride, zirconium nitrate; The titanium salt using is not limited to above-mentioned titanium sulfate, can also be titanium dioxide, titanium sulfate, tetrabutyl titanate; The molysite using is not limited to above-mentioned iron nitrate, can also be ironic hydroxide, ferric sulfate, ferric oxide, iron(ic) chloride; The nickel salt using is not limited to above-mentioned nickelous nitrate, can also be nickel hydroxide, single nickel salt, nickelous chloride, nickel oxide; The cobalt salt using 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 using is not limited to above-mentioned aluminum nitrate, can also be Tai-Ace S 150, aluminium hydroxide, aluminium sesquioxide; Above-mentioned soaking 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 further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.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 obtaining is transferred in retort furnace, under 350 DEG C of conditions, calcined 24 hours, obtain presoma Li 4mn 4.75ti 0.25o 12, the XRD figure of this product is shown in Fig. 1, SEM figure is shown in Fig. 2; From Fig. 1,2, under adopted calcination condition, can obtain the Li of pure phase 4mn 4.75ti 0.25o 12, and product granularity is more even.Get 0.8g presoma and be placed in 200ml0.5mol/L hydrochloric acid soln, put into the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 60 DEG C of still airs dry 3h, 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, under 400 DEG C of conditions, calcine 24 hours, 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 the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 60 DEG C of still airs dry 3h, 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 obtaining is transferred in retort furnace, and calcined 48 hours 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 the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 60 DEG C of still airs dry 3h, 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 obtaining is transferred in retort furnace, and calcined 48 hours 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 the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 60 DEG C of still airs dry 3h, 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 0.8g Li of example 1 4mn 4.75ti 0.25o 12add 200mL0.5mol/L ammonium persulfate solution, put into the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 60 DEG C of still airs dry 3h, 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 0.8g Li of example 1 4mn 4.75ti 0.25o 12add 200mL0.1mol/L HCl solution, put into the hunting of frequency of water bath with thermostatic control vibrator with 130rpm, control homo(io)thermism at 30 DEG C, reaction 12h soaks the Li in presoma +; Further filter, wash completely with deionized water, lead and be less than 10 with the ratio electricity of washings -5Ω -1m -1for standard, suction filtration, in 120 DEG C of still airs dry 8h, 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.Fig. 2 and Fig. 5 are contrasted known, after pickling there is not 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 to add.Be placed in 80 DEG C of stirred in water bath, evaporation drying.The mixture obtaining is transferred in retort furnace, under 450 DEG C of conditions, is calcined 24 hours, cooling after in 1mol/l ammonium persulfate solution wash-out obtain 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, grind evenly; The mixture obtaining is transferred in retort furnace, under 400 DEG C of conditions, is calcined 24 hours, cooling after in 1mol/l hydrochloric acid soln wash-out obtain 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 to add.Be placed in 80 DEG C of stirred in water bath, evaporation drying.The mixture obtaining is transferred in retort furnace, under 450 DEG C of conditions, is calcined 24 hours, cooling after in 1mol/l ammonium persulfate solution wash-out obtain 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
Take respectively the prepared sample ions sieve adsorbant of 100mg example 1,2,3,7,8 and 9 (Doped with Titanium, iron, zirconium, cobalt, al and ni ion respectively) and put into tool sieve Erlenmeyer flask, add 10mL10mmol/L mixed ion solutions (Li +, Na +, K +, Ca 2+, and Mg 2+, pH=10.1), be placed in the hunting of frequency of the large-scale shaking table of intelligent multifunctional with 130rpm, control homo(io)thermism at 30 DEG C, reaction 120h, gets the upper strata stillness of night by the wherein concentration of each ion of IC monitoring, 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, to carrying lithium and Extracting Lithium from Seawater has important practical value in salt lake.
adsorption effect test 2
Take respectively the prepared sample ions sieve of 100mg example 1,3 and 6 and put into tool sieve Erlenmeyer flask, add 100mL Cha Er sweat bittern.Be placed in the hunting of frequency of the large-scale shaking table of intelligent multifunctional with 130rpm, control homo(io)thermism at 30 DEG C, reaction 48h, gets the upper strata stillness of night and monitors the wherein concentration of lithium ion with IC, and 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 respectively the MnO of 100mg example 4 and other ions that undope 20.4H 2the prepared sample ions sieve of O is put into tool sieve Erlenmeyer flask, adds 100mL Cha Er sweat bittern.Be placed in the hunting of frequency of the large-scale shaking table of intelligent multifunctional with 130rpm, control homo(io)thermism at 30 DEG C, reaction 48h, gets the upper strata stillness of night and monitors the wherein concentration of lithium ion with IC, and 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 respectively 0.4% and 2%.This shows by selecting suitable dopant ion and doping not only can effectively improve the adsorptive capacity of ion(ic)sieve to lithium ion, and greatly reduced the molten loss rate of manganese, prepared the more excellent product of stability.
The improvement that it will be appreciated by those skilled in the art that stability is mainly the reduction that is embodied in the molten loss rate of manganese.The molten loss rate of manganese has reduced, and ion(ic)sieve just can use more time, that is to say and has improved stability.
From the various embodiments described above, synthetic method of the present invention, experiment condition, product proportioning are easily controlled, and the condition and range that can obtain desired product is wide; The synthetic ion(ic)sieve sorbent material Mn obtaining of the present invention x/5r y/5o 20.31H 2it can be used for the lithium-containing solution such as salt lake brine, seawater and carries lithium O (wherein R=Sn, Zr, Ti, Fe, Ni, Co or Al), and it is large to have adsorptive capacity, reproducible advantage.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and 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. regulate and control a method for lithium ion sieve stability by cation doping, comprise and prepare 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), by manganous salt, lithium salts and the compound containing R, the mol ratio that makes R/ manganese/lithium is (0.625～0.001): (0.625～1.249): 1.00, and (R+ manganese)/lithium mol ratio is 1.1～1.5;
(2) mixture step (1) being obtained is calcined 6～120h under 350～650 DEG C of dynamic air conditions, obtains 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 hydroxide, lithium chloride or its combination.
4. method according to claim 1, it is characterized in that, in step (1), 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.
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 carried out, and removes moisture before the calcining of carrying out step (2).
6. according to the method described in right 1, it is characterized in that, the mol ratio of R/ manganese/lithium be (0.07～0.16) in step (1): (1.17～1.09): 1, and the temperature of calcining in step (2) is 350～450 DEG C, the time is 12～72h.
7. a method that regulates and controls lithium ion sieve stability by cation doping, comprising: by the composite oxides Li obtaining in claim 1-6 any one 4mn xr yo 12washing, dry, then leach Li through soaking de-agent, obtain the lithium ion sieve Mn of described cation doping x/5R y/5o 20.31H 2o.
8. method as claimed in claim 7, is characterized in that, described in soak hydrochloric acid, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or the ammonium persulphate that de-agent is 0.1～1mol/L.
9. a 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.
10. a 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.
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