CN103227326A - Synthesis method of lithium hexafluorozirconate and new application thereof - Google Patents
Synthesis method of lithium hexafluorozirconate and new application thereof Download PDFInfo
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Abstract
The invention provides a synthesis method of lithium hexafluorozirconate and its new application. The synthesis method comprises the steps of: firstly, preparing a transparent fluorozirconic acid solution; secondly, preparing lithium fluoride into a 20-30% lithium fluoride suspension liquid by using pure water; thirdly, adding the lithium fluoride suspension liquid obtained in the second step into the transparent fluorozirconic acid solution prepared in the first step in a dropwise manner, thus obtaining a white and turbid lithium hexafluorozirconate suspension liquid; and fourthly, stirring and heating the lithium hexafluorozirconate suspension liquid prepared in the third step to make water in the lithium hexafluorozirconate suspension liquid evaporated and make the suspension liquid concentrated, when the suspension liquid becomes fully white and turbid, conducting filtering, washing a filter cake by pure water and performing crystallization, then placing crystals on a PTFE board, implementing heating and drying, naturally cooling the crystals, and carrying out grinding and crushing, thus obtaining lithium hexafluorozirconate powder. The synthesized lithium hexafluorozirconate has high purity, and when it is applied to a lithium battery electrolyte solution containing lithium hexafluorophosphate, conductivity of the lithium battery electrolyte solution is significantly enhanced, so that the lithium battery performance can be improved.
Description
Technical field
The invention belongs to the Study on Li-ion batteries using technical field, be specifically related to a kind of synthetic method and new purposes thereof of hexafluoro zirconate lithium.
Background technology
Lithium ion battery has energy density than characteristics such as big, that carrying capacity of environment is little, therefore, is widely used in portable electric appts, large-scale application is in electric automobile in the future, fields such as energy-accumulating power station.
Electrolyte is to finish the indispensable part of electrochemical reaction as one of important component part of lithium ion battery.In the prior art, mainly adopt lithium hexafluoro phosphate as electrolyte, its conductive capability is still limited, thereby can reduce the performance of lithium ion battery.
Summary of the invention
Defective at the prior art existence, the invention provides a kind of synthetic method and new purposes thereof of hexafluoro zirconate lithium, the purity height of the hexafluoro zirconate lithium that is synthesized, in the time of in applying it to the lithium battery electrolytes that contains lithium hexafluoro phosphate, obviously strengthen the conductivity of lithium battery electrolytes, thereby improve the performance of lithium battery.
The technical solution used in the present invention is as follows:
The present invention's first purpose is to provide a kind of synthetic method of hexafluoro zirconate lithium, may further comprise the steps:
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as the suspension-turbid liquid of 15-25%, stirs this suspension-turbid liquid, drips the hydrofluoric acid of 60-70% in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as the lithium carbonate suspension-turbid liquid of 20-30% with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped the hydrofluoric acid of 60-70% in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as the lithium fluoride suspension-turbid liquid of 20-30% with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
The 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes, water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid is concentrated, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, then crystallization is positioned over heating, drying on the PTFE plate, grinds behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
Preferably, described filter cake is specially with the pure water wash crystallization:
Filter cake is placed in the centrifuge tube, in centrifuge tube, adds pure water; 25 ℃ of centrifugal 0.5-1h left standstill 5-8 hour, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 10: 1-15: 1.
Preferably, in the 4th step, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours.
In the prior art, disclose and a kind of lithium hydroxide or lithium chloride or lithium carbonate solution or suspension-turbid liquid are added drop-wise in the hexafluoro zirconate lithium solution that has been mixed with, thereby prepare the hexafluoro zirconate lithium.But the purity of the preparation-obtained hexafluoro zirconate lithium of this kind method is lower.And adopt preparation method provided by the invention, can make the very high hexafluoro zirconate lithium of purity.The final products that the present invention is prepared carry out the test of X-ray powder diffraction, by the collection of illustrative plates of Fig. 1 gained, have verified that final products are the hexafluoro zirconate lithium.Its purity is 97.8%.
The present invention's second purpose is to provide the new purposes of the hexafluoro zirconate lithium that a kind of method for preparing obtains, and described hexafluoro zirconate lithium is added contain in the lithium battery electrolytes of lithium hexafluoro phosphate; Wherein, described lithium hexafluoro phosphate is main electrolyte, and described hexafluoro zirconate lithium is an assisted electrolysis matter.
Preferably, in described lithium battery electrolytes, the mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1-10: 2.
Preferably, the mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.5.
Preferably, in the lithium battery electrolytes, organic solvent is one or more among ethylene carbonate EC, diethyl carbonate DEC, dimethyl carbonate DMC, propene carbonate PC and the methyl ethyl carbonate MEC.
The inventor is devoted for years to the research in lithium battery electrolytes, through after the experiment repeatedly, the unexpected discovery is when adding a certain proportion of hexafluoro zirconate lithium in the lithium battery electrolytes that contains lithium hexafluoro phosphate, can obviously improve the conductivity of lithium battery electrolytes, thereby improve the performance of lithium battery.Follow-up comparative example 2 has proved this conclusion.
Description of drawings
The X-ray powder diffraction pattern of the hexafluoro zirconate lithium that Fig. 1 prepares for the present invention.
Embodiment
The hexafluoro zirconate lithium prepares embodiment one
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 20% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 65% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 25% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 65% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 25% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 0.8h left standstill 7 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 12: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.8%.
The hexafluoro zirconate lithium prepares embodiment two
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 15% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 70% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 30% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 60% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 30% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 1h left standstill 5 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 10: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.9%.
The hexafluoro zirconate lithium prepares embodiment three
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 25% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 60% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 20% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 70% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 20% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 0.5h left standstill 8 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 15: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.8%.
The hexafluoro zirconate lithium prepares embodiment four
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 18% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 63% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 24% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 67% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 28% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 0.9h left standstill 6 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 14: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.9%.
The hexafluoro zirconate lithium prepares embodiment five
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 19% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 63% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 27% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 62% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 26% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 0.9h left standstill 7 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 11: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.9%.
The hexafluoro zirconate lithium prepares embodiment six
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as 23% suspension-turbid liquid, stirs this suspension-turbid liquid, drips 62% hydrofluoric acid in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as 23% lithium carbonate suspension-turbid liquid with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped 66% hydrofluoric acid in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as 28% lithium fluoride suspension-turbid liquid with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
In the 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes concentrates the water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, wherein, crystallization condition is: filter cake is placed in the centrifuge tube, adds pure water in centrifuge tube; 25 ℃ of centrifugal 0.9h left standstill 6 hours, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 11: 1;
Then crystallization is positioned over heating, drying on the PTFE plate, wherein, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours; Grind behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
The purity of the hexafluoro zirconate lithium powder that method for preparing obtains is 97.8%.
Purposes embodiment one
The hexafluoro zirconate lithium that preparation embodiment one is prepared joins in the lithium battery electrolytes that contains lithium hexafluoro phosphate; Wherein, the organic solvent in the lithium battery electrolytes is PC; The mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.0, and concentration is respectively 1.0mol/l and 0.10mol/l.
Purposes embodiment two
The hexafluoro zirconate lithium that preparation embodiment three is prepared joins in the lithium battery electrolytes that contains lithium hexafluoro phosphate; Wherein, the organic solvent in the lithium battery electrolytes is diethyl carbonate DEC; The mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.2, and concentration is respectively 1.0mol/l and 0.12mol/l.
Purposes embodiment three
The hexafluoro zirconate lithium that preparation embodiment six is prepared joins in the lithium battery electrolytes that contains lithium hexafluoro phosphate; Wherein, the organic solvent in the lithium battery electrolytes is dimethyl carbonate DMC; The mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.8, and concentration is respectively 1.0mol/l and 0.18mol/l.
Purposes embodiment four
The hexafluoro zirconate lithium that preparation embodiment six is prepared joins in the lithium battery electrolytes that contains lithium hexafluoro phosphate; Wherein, the organic solvent in the lithium battery electrolytes is ethylene carbonate EC; The mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.4, and concentration is respectively 1.0mol/l and 0.14mol/l.
Purposes embodiment five
The hexafluoro zirconate lithium that preparation embodiment six is prepared joins in the lithium battery electrolytes that contains lithium hexafluoro phosphate; Wherein, the organic solvent in the lithium battery electrolytes is methyl ethyl carbonate MEC; The mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.6, and concentration is respectively 1.0mol/l and 0.16mol/l.
Test example 1
This test example is used to investigate the preparation-obtained electrolyte of purposes embodiment 1-5 20 ℃ molar conductivity, the results are shown in Table 1.
Table 1
| Numbering | Molar conductivity 0.0001Sm2/mol |
| Purposes embodiment one | 8.5 |
| Purposes embodiment two | 8.4 |
| Purposes embodiment three | 8.4 |
| Purposes embodiment four | 8.5 |
| Purposes embodiment five | 8.6 |
Comparative example 1
This comparative example is used to investigate the influence to the conductivity and the molar conductivity of electrolyte of hexafluoro zirconate lithium and lithium hexafluoro phosphate proportioning.
As shown in table 2, prepare following 7 kinds of electrolyte respectively, measure the electric conductivity of 7 kinds of electrolyte being prepared under 20 ℃ respectively.Wherein, electrolyte 2 to 7 employed hexafluoro zirconate lithiums are embodiment one preparation gained.
Table 2
Annotate: molar conductivity=conductivity ÷ total electrolyte content
As can be seen from the above table, under the constant situation of the organic solvent of electrolyte and main electrolyte hexafluorophosphoric acid lithium content, only change the content of assisted electrolysis matter hexafluoro zirconate lithium, the molar conductivity of electrolyte changes greatly.Concrete, when not adding assisted electrolysis matter hexafluoro zirconate lithium in the electrolyte, the molar conductivity minimum of electrolyte; Along with the increase of hexafluoro zirconate lithium content, the molar conductivity of electrolyte increases gradually, and when hexafluoro zirconate lithium mole was 0.15 times of lithium hexafluoro phosphate mole, the molar conductivity of electrolyte was the highest; When continuing to increase the hexafluoro zirconate lithium content then, the molar conductivity of electrolyte descends on the contrary.Therefore, the optimum mole ratio of hexafluoro zirconate lithium and lithium hexafluoro phosphate is 0.15: 1.
The hexafluoro zirconate lithium that other embodiments of the invention are prepared has carried out identical test, and experimental result is close.
Comparative example 2
This comparative example is used for conductivity (mS/cm) and the molar conductivity (0.0001Sm of more various electrolyte under different temperatures
2/ mol), wherein, numbering 1-7 is electrolyte used in the comparative example 1.
Table 3
As can be seen from the above table, temperature-20 spend to 40 the degree four temperature sections the time conductivity value all increase along with the increase of assisted electrolysis matter addition.
When hexafluoro zirconate lithium mole was 0.15 times of lithium hexafluoro phosphate mole, the molar conductivity of the electrolyte of four temperature sections all was a maximum.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be looked protection scope of the present invention.
Claims (7)
1. the synthetic method of a hexafluoro zirconate lithium is characterized in that, may further comprise the steps:
The first step, with pure water with zirconium dioxide ZrO
2Powder is formulated as the suspension-turbid liquid of 15-25%, stirs this suspension-turbid liquid, drips the hydrofluoric acid of 60-70% in suspension-turbid liquid, makes transparent fluorine zirconic acid H
2ZrF
6Solution;
Second step was formulated as the lithium carbonate suspension-turbid liquid of 20-30% with pure water with the lithium carbonate powder, stirred this suspension-turbid liquid, dripped the hydrofluoric acid of 60-70% in suspension-turbid liquid, made the lithium fluoride suspension-turbid liquid; Filter the lithium fluoride suspension-turbid liquid, after filter cake washed with pure water, getting filter cake was lithium fluoride, lithium fluoride is formulated as the lithium fluoride suspension-turbid liquid of 20-30% with pure water;
The 3rd step with the lithium fluoride suspension-turbid liquid that the preparation of second step obtains, was added drop-wise to the first step and prepares in the transparent fluorine zirconic acid solution that obtains, and preparation obtains the hexafluoro zirconate lithium suspension-turbid liquid of gonorrhoea;
The 4th step, the hexafluoro zirconate lithium suspension-turbid liquid that the 3rd step of agitating heating makes, water evaporates in the hexafluoro zirconate lithium suspension-turbid liquid is concentrated, treat to filter after the abundant gonorrhoea of suspension-turbid liquid, with the crystallization of pure water washing leaching cake, then crystallization is positioned over heating, drying on the PTFE plate, grinds behind the natural cooling, promptly obtain the hexafluoro zirconate lithium powder.
2. the synthetic method of hexafluoro zirconate lithium according to claim 1 is characterized in that, described filter cake is specially with the pure water wash crystallization:
Filter cake is placed in the centrifuge tube, in centrifuge tube, adds pure water; 25 ℃ of centrifugal 0.5-1h left standstill 5-8 hour, separated out crystallization; Wherein, the mass ratio of filter cake and pure water is 10: 1-15: 1.
3. the synthetic method of hexafluoro zirconate lithium according to claim 1 is characterized in that, in the 4th step, the heating, drying condition is: at first be heated to 60 degree oven dry 2 hours, and then be heated to 110 degree oven dry 2 hours.
4. the new purposes of each hexafluoro zirconate lithium for preparing of claim 1-3 is characterized in that, described hexafluoro zirconate lithium is added contain in the lithium battery electrolytes of lithium hexafluoro phosphate; Wherein, described lithium hexafluoro phosphate is main electrolyte, and described hexafluoro zirconate lithium is an assisted electrolysis matter.
5. the new purposes of hexafluoro zirconate lithium according to claim 4 is characterized in that, in described lithium battery electrolytes, the mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1-10: 2.
6. the new purposes of hexafluoro zirconate lithium according to claim 5 is characterized in that, the mol ratio of lithium hexafluoro phosphate and hexafluoro zirconate lithium is 10: 1.5.
7. the new purposes of hexafluoro zirconate lithium according to claim 4, it is characterized in that, in the lithium battery electrolytes, organic solvent is one or more among ethylene carbonate EC, diethyl carbonate DEC, dimethyl carbonate DMC, propene carbonate PC and the methyl ethyl carbonate MEC.
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| CN106117217A (en) * | 2016-06-08 | 2016-11-16 | 南京远淑医药科技有限公司 | A kind of preparation method of fluozirconate |
| CN110092417A (en) * | 2019-04-17 | 2019-08-06 | 南通金星氟化学有限公司 | A kind of preparation method of potassium fluorozirconate |
| CN112670563A (en) * | 2020-12-30 | 2021-04-16 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN113422110A (en) * | 2021-06-29 | 2021-09-21 | 华南理工大学 | Synthesis method of mixed zirconium salt electrolyte material and application of mixed zirconium salt electrolyte material in lithium metal battery |
| CN113929136A (en) * | 2021-09-27 | 2022-01-14 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium fluorozirconate |
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| CN106117217A (en) * | 2016-06-08 | 2016-11-16 | 南京远淑医药科技有限公司 | A kind of preparation method of fluozirconate |
| CN106117217B (en) * | 2016-06-08 | 2018-07-10 | 南京远淑医药科技有限公司 | A kind of preparation method of fluozirconate |
| CN110092417A (en) * | 2019-04-17 | 2019-08-06 | 南通金星氟化学有限公司 | A kind of preparation method of potassium fluorozirconate |
| CN112670563A (en) * | 2020-12-30 | 2021-04-16 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN112670563B (en) * | 2020-12-30 | 2022-05-17 | 广东微电新能源有限公司 | Solid electrolyte material, preparation method thereof and solid battery |
| CN113422110A (en) * | 2021-06-29 | 2021-09-21 | 华南理工大学 | Synthesis method of mixed zirconium salt electrolyte material and application of mixed zirconium salt electrolyte material in lithium metal battery |
| CN113422110B (en) * | 2021-06-29 | 2022-03-29 | 华南理工大学 | Synthesis method of mixed zirconium salt electrolyte material and application of mixed zirconium salt electrolyte material in lithium metal battery |
| WO2023273077A1 (en) * | 2021-06-29 | 2023-01-05 | 华南理工大学 | Method for synthesizing mixed zirconium salt electrolyte material and use thereof in lithium metal battery |
| CN113929136A (en) * | 2021-09-27 | 2022-01-14 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium fluorozirconate |
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Effective date of registration: 20170810 Address after: 342600 fluorine salt chemical industry base of Huichang County, Jiangxi, Ganzhou Patentee after: Jiangxi Shi Lei Fluorine Material Co., Ltd. Address before: 100176, Beijing, Beijing economic and Technological Development Zone, Zhonghe street, No. 1, building 415-1, room four, 14, Co-patentee before: Shi Shikun Patentee before: Beijing Shilei Qiankun Fluorinated New Materials Research Institute Co., Ltd. |