CN103204541B - Synthesis method and novel application of hexafluorine lithium titanate - Google Patents
Synthesis method and novel application of hexafluorine lithium titanate Download PDFInfo
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Abstract
The invention provides a synthesis method and novel application of hexafluorine lithium titanate. The synthesis method comprises the following steps of: step one, preparing a transparent fluorine lithium titanate H2TiF6 solution; step two, preparing a lithium fluoride suspension, filtering the lithium fluoride suspension, taking the filter cake, namely, the lithium fluoride, preparing the lithium fluoride into a 20-30% lithium fluoride suspension by using pure water; step three, dropping the lithium fluoride suspension prepared in the step two into the transparent fluorine lithium titanate solution prepared in the step one, and preparing so as to obtain a transparent hexafluorine lithium titanate solution; and step four, stirring and heating the hexafluorine lithium titanate solution prepared in the step three, washing and crystallizing the filter cake by using pure water, heating and drying the crystal, naturally cooling down and grinding and crushing so as to obtain hexafluorine lithium titanate powder. The synthesized hexafluorine lithium titanate is high in purity, and when the hexafluorine lithium titanate is applied to lithium battery electrolyte with the hexafluorine lithium, the conductivity of the battery electrolyte is greatly improved, so that the performance of a lithium battery is improved.
Description
Technical field
The invention belongs to Study on Li-ion batteries technical field, be specifically related to a kind of preparation method and use of hexafluorotitanic acid lithium.
Background technology
Lithium ion battery has the features such as energy density ratio is large, carrying capacity of environment is little, therefore, is widely used in portable electric appts, in the future large-scale application in electromobile, the fields such as energy-accumulating power station.
Ionogen, as one of the important component part of lithium ion battery, has been the indispensable part of electrochemical reaction.In prior art, the main lithium hexafluoro phosphate that adopts is as ionogen, and its conductive capability is still limited, thus can reduce the performance of lithium ion battery.
In prior art, disclose and a kind of lithium hydroxide or lithium chloride or Lithium carbonate solution or suspension liquid to be added drop-wise in the hexafluorotitanic acid lithium solution be mixed with, thus prepare hexafluorotitanic acid lithium.But the purity of this kind of method preparation-obtained hexafluorotitanic acid lithium is lower.And adopt preparation method provided by the invention, the hexafluorotitanic acid lithium that purity is very high can be obtained.The test of X-ray powder diffraction is carried out to the finished product that the present invention prepares, by the collection of illustrative plates of Fig. 1 gained, demonstrates the finished product and be hexafluorotitanic acid lithium.Its purity is 97.8%.
The present invention second object is the purposes of the hexafluorotitanic acid lithium providing a kind of aforesaid method to prepare, and adds in the lithium battery electrolytes containing lithium hexafluoro phosphate by described hexafluorotitanic acid lithium; Wherein, described lithium hexafluoro phosphate is main ionogen, and described hexafluorotitanic acid lithium is assisted electrolysis matter.
Preferably, in described lithium battery electrolytes, the mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1-10: 2.
Preferably, the mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.5.
Preferably, in lithium battery electrolytes, organic solvent is one or more in NSC 11801 EC, diethyl carbonate DEC, methylcarbonate DMC, propylene carbonate PC and Methyl ethyl carbonate MEC.
The present inventor is devoted for years to the research in lithium battery electrolytes, after many experiments, unexpected to find, when to when adding a certain proportion of hexafluorotitanic acid lithium in containing the lithium battery electrolytes of lithium hexafluoro phosphate, the electroconductibility of lithium battery electrolytes can be significantly improved, thus improve the performance of lithium cell.Follow-up comparative example 2 demonstrates this conclusion.
Summary of the invention
For the defect that prior art exists, the invention provides a kind of preparation method and use of hexafluorotitanic acid lithium, the purity of synthesized hexafluorotitanic acid lithium is high, when applying it in the lithium battery electrolytes containing lithium hexafluoro phosphate, the electroconductibility of obvious enhancing lithium battery electrolytes, thus the performance improving lithium cell.
The technical solution used in the present invention is as follows:
The present invention first object is the synthetic method providing a kind of hexafluorotitanic acid lithium, comprises the following steps:
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 15-25%, under heated and stirred, drips the hydrofluoric acid of 60-70% in titanium dioxide suspension liquid, obtained transparent hydrofluotitanic acid H
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 20-30% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 60-70% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 20-30%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, moisture in hexafluorotitanic acid lithium solution is evaporated, solution concentrates, filter after solution gonorrhoea, filter cake pure water crystallization, is then positioned over heating, drying on PTFE plate by crystallization, grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
Preferably, the crystallization of described filter cake pure water is specially:
Filter cake is placed in centrifuge tube, in centrifuge tube, adds pure water; 25 DEG C of centrifugal 0.5-1h, leave standstill 5-8 hour, crystallization; Wherein, the mass ratio of filter cake and pure water is 10: 1-15: 1.
Preferably, in the 4th step, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction pattern of the hexafluorotitanic acid lithium that the present invention prepares.
Embodiment
Hexafluorotitanic acid lithium prepares embodiment one
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 15%, under heated and stirred, drips the hydrofluoric acid of 70%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 20% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 70% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 20%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 1h, leave standstill 8 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 10: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 97.8%.
Hexafluorotitanic acid lithium prepares embodiment two
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 25%, under heated and stirred, drips the hydrofluoric acid of 60%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 30% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 60% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 30%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 1h, leave standstill 5 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 15: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 98.1%.
Hexafluorotitanic acid lithium prepares embodiment three
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 20%, under heated and stirred, drips the hydrofluoric acid of 65%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 25% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 65% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 25%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 0.7h, leave standstill 7 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 12: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 98.3%.
Hexafluorotitanic acid lithium prepares embodiment four
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 18%, under heated and stirred, drips the hydrofluoric acid of 62%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 23% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 67% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 24%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 0.7h, leave standstill 6 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 12: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 97.7%.
Hexafluorotitanic acid lithium prepares embodiment five
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 22%, under heated and stirred, drips the hydrofluoric acid of 65%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 27% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 67% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 23%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 0.6h, leave standstill 7 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 14: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 97.5%.
Hexafluorotitanic acid lithium prepares embodiment six
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 18%, under heated and stirred, drips the hydrofluoric acid of 64%, obtained transparent hydrofluotitanic acid H in titanium dioxide suspension liquid
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 23% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 68% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 27%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, makes the moisture in hexafluorotitanic acid lithium solution evaporate, solution concentrates, and filters, filter cake pure water crystallization after solution gonorrhoea, crystallization condition is: be placed into by filter cake in centrifuge tube, in centrifuge tube, add pure water; 25 DEG C of centrifugal 0.8h, leave standstill 7 hours, crystallization; Wherein, the mass ratio of filter cake and pure water is 12: 1;
Then crystallization is positioned over heating, drying on PTFE plate, wherein, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours; Grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder.
The purity of the hexafluorotitanic acid lithium powder that aforesaid method prepares is 97.9%.
Purposes embodiment one
The hexafluorotitanic acid lithium that preparation embodiment one prepares is joined in the lithium battery electrolytes containing lithium hexafluoro phosphate; Wherein, the organic solvent in lithium battery electrolytes is PC; The mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.5, and concentration is respectively 1.0mol/l and 0.15mol/l.
Purposes embodiment two
The hexafluorotitanic acid lithium that preparation embodiment three prepares is joined in the lithium battery electrolytes containing lithium hexafluoro phosphate; Wherein, the organic solvent in lithium battery electrolytes is diethyl carbonate DEC; The mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.2, and concentration is respectively 1.0mol/l and 0.12mol/l.
Purposes embodiment three
The hexafluorotitanic acid lithium that preparation embodiment six prepares is joined in the lithium battery electrolytes containing lithium hexafluoro phosphate; Wherein, the organic solvent in lithium battery electrolytes is methylcarbonate DMC; The mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.8, and concentration is respectively 1.0mol/l and 0.18mol/l.
Purposes embodiment four
The hexafluorotitanic acid lithium that preparation embodiment six prepares is joined in the lithium battery electrolytes containing lithium hexafluoro phosphate; Wherein, the organic solvent in lithium battery electrolytes is NSC 11801 EC; The mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.4, and concentration is respectively 1.0mol/l and 0.14mol/l.
Purposes embodiment five
The hexafluorotitanic acid lithium that preparation embodiment six prepares is joined in the lithium battery electrolytes containing lithium hexafluoro phosphate; Wherein, the organic solvent in lithium battery electrolytes is Methyl ethyl carbonate MEC; The mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10: 1.6, and concentration is respectively 1.0mol/l and 0.16mol/l.
Test example 1
This test example, for investigating the preparation-obtained electrolytic solution of purposes embodiment 1-5 the molecular conductivity of 20 DEG C, the results are shown in Table 1.
Table 1
| Numbering | Molecular conductivity 0.0001Sm2/mol |
| Purposes embodiment one | 8.3 |
| Purposes embodiment two | 8.1 |
| Purposes embodiment three | 8.4 |
| Purposes embodiment four | 8.5 |
| Purposes embodiment five | 8.2 |
Comparative example 1
This comparative example is for investigating hexafluorotitanic acid lithium and the specific conductivity of lithium hexafluoro phosphate proportioning on electrolytic solution and the impact of molecular conductivity.
As shown in table 2, the following 7 kinds of electrolytic solution of preparation, measure the conductivity of the 7 kinds of electrolytic solution prepared respectively at 20 DEG C respectively.Wherein, the hexafluorotitanic acid lithium that uses of electrolytic solution 2 to 7 prepares gained for embodiment one.
Table 2
Note: molecular conductivity=specific conductivity ÷ total electrolyte content
As can be seen from the above table, when the organic solvent of electrolytic solution and main ionogen phosphofluoric acid lithium content constant, only change the content of assisted electrolysis matter hexafluorotitanic acid lithium, the molecular conductivity of electrolytic solution changes greatly.Concrete, when not adding assisted electrolysis matter hexafluorotitanic acid lithium in electrolytic solution, the molecular conductivity of electrolytic solution is minimum; Along with the increase of hexafluorotitanic acid lithium content, the molecular conductivity of electrolytic solution increases gradually, and when hexafluorotitanic acid lithium molar weight is 0.15 times of lithium hexafluoro phosphate molar weight, the molecular conductivity of electrolytic solution is the highest; When then continuing to increase hexafluorotitanic acid lithium content, the molecular conductivity of electrolytic solution declines on the contrary.Therefore, the optimum mole ratio of hexafluorotitanic acid lithium and lithium hexafluoro phosphate is 0.15: 1.
Carried out identical test to the hexafluorotitanic acid lithium that other embodiments of the invention prepare, experimental result is similar.
Comparative example 2
This comparative example is used for more various electrolytic solution specific conductivity at different temperatures (mS/cm) and molecular conductivity (0.0001Sm
2/ mol), wherein, numbering 1-7 is electrolytic solution used in comparative example 1.
Table 3
As can be seen from the above table, temperature all increases along with the increase of assisted electrolysis matter addition to conductivity value during four temperature sections of 40 degree at-20 degree.
When hexafluorotitanic acid lithium molar weight is 0.15 times of lithium hexafluoro phosphate molar weight, the molecular conductivity of the electrolytic solution of four temperature sections is all maximum value.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should look protection scope of the present invention.
Claims (2)
1. a synthetic method for hexafluorotitanic acid lithium, is characterized in that, comprises the following steps:
The first step, with pure water by titanium dioxide TiO
2powder is formulated as the suspension liquid of 15-25%, under heated and stirred, drips the hydrofluoric acid of 60-70% in titanium dioxide suspension liquid, obtained transparent hydrofluotitanic acid H
2tiF
6solution;
Second step, is formulated as the Quilonum Retard suspension liquid of 20-30% by lithium carbonate powder with pure water, under heated and stirred, drip the hydrofluoric acid of 60-70% in Quilonum Retard suspension liquid, obtained lithium fluoride suspension liquid; Filter lithium fluoride suspension liquid, after filter cake pure water, get filter cake and lithium fluoride, with pure water, lithium fluoride is formulated as the lithium fluoride suspension liquid of 20-30%;
3rd step, prepares the lithium fluoride suspension liquid obtained by second step, be added drop-wise to the first step and prepare in the transparent hydrofluotitanic acid solution obtained, and preparation obtains transparent hexafluorotitanic acid lithium solution;
4th step, the transparent hexafluorotitanic acid lithium solution that stirring heating the 3rd step obtains, moisture in hexafluorotitanic acid lithium solution is evaporated, solution concentrates, filter after solution gonorrhoea, filter cake pure water crystallization, is then positioned over heating, drying on PTFE plate by crystallization, grind after naturally cooling, namely obtain hexafluorotitanic acid lithium powder;
Wherein, the crystallization of described filter cake pure water is specially:
Filter cake is placed in centrifuge tube, in centrifuge tube, adds pure water; 25 DEG C of centrifugal 0.5-1h, leave standstill 5-8 hour, crystallization; Wherein, the mass ratio of filter cake and pure water is 10:1-15:1;
Wherein, in the 4th step, heating, drying condition is: be first heated to 60 degree and dry 2 hours, and then is heated to 110 degree and dries 2 hours.
2. the purposes of hexafluorotitanic acid lithium for preparing of the synthetic method of hexafluorotitanic acid lithium according to claim 1, is characterized in that, add in the lithium battery electrolytes containing lithium hexafluoro phosphate by described hexafluorotitanic acid lithium; Wherein, described lithium hexafluoro phosphate is main ionogen, and described hexafluorotitanic acid lithium is assisted electrolysis matter;
Wherein, the mol ratio of lithium hexafluoro phosphate and hexafluorotitanic acid lithium is 10:1.5;
Wherein, in lithium battery electrolytes, organic solvent is one or more in NSC 11801 EC, diethyl carbonate DEC, methylcarbonate DMC, propylene carbonate PC and Methyl ethyl carbonate MEC.
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Non-Patent Citations (2)
| Title |
|---|
| On the room temperature synthesis of monoclinic Li3FeF6: A new cathode material for rechargeable lithium batteries;E. Gonzalo et al.;《Journal of Power Sources》;20100220;第195卷;第4991页 * |
| Preparation, Crystal Structure, and Magnetic Properties of P-Li3TiF6 = Li2[4]Li7[6](TiF6)(TiF6)2-a Double Fluoride?;Avesh K. Tyagi et al.;《Z. anorg. allg. Chem.》;19961231;第622卷;第1329页 * |
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Effective date of registration: 20220412 Address after: 342600 Fluoride Salt Chemical Industry Base, Huichang County, Ganzhou City, Jiangxi Province Patentee after: Jiangxi Shi Lei Fluorine Material Co.,Ltd. Address before: 342614 fluoride chemical industry base, junmenling Town, Huichang County, Ganzhou City, Jiangxi Province Patentee before: JIANGXI SHILEI FLUORINE CHEMICAL Co.,Ltd. |
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