CN1711214A - Method for producing fluorine-containing lithium compound - Google Patents
Method for producing fluorine-containing lithium compound Download PDFInfo
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- CN1711214A CN1711214A CNA2003801029929A CN200380102992A CN1711214A CN 1711214 A CN1711214 A CN 1711214A CN A2003801029929 A CNA2003801029929 A CN A2003801029929A CN 200380102992 A CN200380102992 A CN 200380102992A CN 1711214 A CN1711214 A CN 1711214A
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- Prior art keywords
- fluorine
- lif
- lithium compound
- containing lithium
- reaction
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/006—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/02—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A method for simply producing an LiMFx which is free from impurities such as HF and other by-products that adversely affect battery performance is disclosed. The method for producing a fluorine-containing lithium compound which can be represented by a certain general formula is characterized in that LiF is brought into contact with an element M (M is an element selected from the group consisting of B, P, As, Sb, Bi, V, Nb, and Ta) and/or a fluoride of the element M in the presence of fluorine gas.
Description
Technical field
The present invention relates to a kind of method for preparing fluorine-containing lithium compound, described fluorine-containing lithium compound is by formula LiMF
xShown in (M represents to be selected from the element of B, P, As, Sb, Bi, V, Nb and Ta, and x represents 4～6 number), particularly, the present invention relates to a kind of easy preparation LiMF
xMethod, this LiMF
xContain hardly battery performance is produced dysgenic impurity such as HF or other by product.
Prepared in accordance with the present invention by formula LiMF
xShown compound is a kind of very useful ionogen, is used in particular for the ionogen of lithium cell and lithium ion battery.
Background technology
In recent years, fast as the spreading speed of portable phone, portable data assistance or notebook PC because the digital mobile electronic machine, the demand of energy accumulating device such as lithium ion battery is increased sharply.And, consider environmental problem or energy-conservation, these energy accumulating devices arouse attention as the power supply of PEV (pure electric vehicle) or HEV (hybrid electric vehicle).
These energy accumulating devices need electrolytic solution as component.Frequent use wherein has electrolytic solution to be dissolved in organic electrolyte solution in the non-aqueous solvent as this electrolytic solution, to move under high operating voltage.
In lithium ion chargeable battery, for example, as negative pole, and in the lithium ion chargeable battery of use lithium transition-metal oxide as the anodal main component, use special electrolyte solution at the compound that uses lithium metal or lithium and carbon or other metal except that lithium.Will be as electrolytical LiPF
6, LiBF
4Deng in the mixed solvent that is dissolved in cyclic carbonate (as ethylene carbonate or Texacar PC) and linear carbonate (as methylcarbonate, Methyl ethyl carbonate or diethyl carbonate) (for example, seeing non-patent document 1).
At the electrolyte solution that is used for lithium ion battery that uses those non-aqueous solvents, because non-aqueous solvent and electrolytical high electrochemical stability, so battery can use under high-voltage.Yet, still need to design battery with high electrochemical stability.Therefore, when electrolyte solution during by contaminating impurity, compare with ionogen with relevant non-aqueous solvent, nearly all these impurity only have low electrochemical stability.Therefore, these impurity cause the deterioration of battery performance easily at the battery internal reaction.
Therefore, the described non-aqueous solvent and the electrolytic solution of these electrolyte solutions of expectation formation are impure hardly.
Alkyl) etc. and HPF incidentally, by LiOH, LiOR (R:
6Reaction is by the preparation LiPF of the mode similar to the preparation ordinary salt
6Method, the ionogen LiPF of just usually said preparation lithium ion battery special use
6Method.Yet in the method, the product that forms by hydrolysis is as impurity and LiPF
6Mix.What therefore, carry out usually is to make LiF and PF
5The production method (for example, seeing patent document 1～4) of reaction.
The PF that is used for this reaction
5Generally by the ligand exchange preparation, described ligand exchange is to pass through PF
5Outside pentavalent phosphorous compound such as PCl
5Carry out with the HF reaction; Perhaps by oxidation trivalent phosphorous compound such as PCl
3, then carry out ligand exchange and prepare with HF.Also often adopt in the following method, wherein successively be prepared PF
5Reaction and gained PF
5Reaction (for example, seeing patent document 5～10) with LiF.
Yet, in reaction, adopting in the method for HF at these, HF is adsorbed on the LiPF of gained probably
6Go up and remain.All derive from the by product of original ligand, also remain as impurity as HF as the HCl that forms as by product.And these impurity need to handle, fully to remove them after reaction, because impurity is for the performance generation detrimentally affect of battery.
In recent years, new production method has been proposed, to solve these problems from the impurity of HF.For example, the method that has proposed to prepare LiF and P from other inorganic fluoride (for example, see patent document 11), but produced and removed the inorganic fluoride that is used to react, or after reaction, eliminate fluorine and the relevant other problem of inorganics that forms, although this method has not obtained advantage because of not using HF.And, also proposed at F
2Exist down, make LiCl and PCl
5The method (for example, seeing patent document 12) of reaction, but still have the problem of by-product HCl, although this method adopts the F that removes easily
2(rather than HF).
[patent document 1]
The specification sheets of US 3607020
[patent document 2]
The specification sheets of JP-A-9-165210
[patent document 3]
The brochure that No. the 2000/010917th, the PCT international publication
[patent document 4]
The specification sheets of JP-A-2001-122604
[patent document 5]
The specification sheets of JP-A-4-175216
[patent document 6]
The specification sheets of JP-A-5-279003
[patent document 7]
The specification sheets of JP-A-6-056413
[patent document 8]
The brochure that No. the 98/06666th, the PCT international publication
[patent document 9]
The specification sheets of EP-A-4-846657
[patent document 10]
The specification sheets of JP-A-11-171518
[patent document 11]
The specification sheets of JP-A-2001-122605
[patent document 12]
The specification sheets that No. the 10027211st, German patent publication
[non-patent document 1]
M.Ukei，et?al.，“Development?and?Market?of?Materials?for?Lithium?IonBatteries”(CMC)Chapter?6(1997)
Summary of the invention
The objective of the invention is to solve above-mentioned general issues, and a kind of preparation LiMF is provided
xMethod, this LiMF
xThe performance that contains hardly battery produces dysgenic impurity such as HF or its by product, and this method is preparation formula LiMF
xThe method of the fluorine-containing lithium compound shown in (M represents to be selected from the element of B, P, As, Sb, Bi, V, Nb and Ta, and x represents 4～6 number).
At preparation formula LiMF
x(M represents to be selected from one or both or the multiple element among B, P, As, Sb, Bi, V, Nb and the Ta, x represents 4～6 number) shown in the method for fluorine-containing lithium compound in, the method for preparing fluorine-containing lithium compound of the present invention is characterised in that, in single reactor, under the situation that fluorine gas exists, LiF is contacted with element M, LiF is contacted or the fluorochemical of element M and the mixture of element M contact with the fluorochemical of element M.
Through further investigation, the inventor finds, contains the LiMF that the performance of lithium ion battery is produced dysgenic impurity such as HF or HCl hardly
xCan prepare by the following method: in single reactor, under the situation that fluorine gas exists, preferably under 100 ℃ or higher temperature, LiF is contacted with element M, LiF and the fluorochemical of element M or the fluorochemical of element M and the mixture of element M are contacted, that is, under the LiF coexistence by element M and F
2Reaction, fluorochemical and F by element M under LiF coexistence
2Reaction, perhaps fluorochemical and the F by element M and element M under LiF coexistence
2Reaction, realize the present invention.
Embodiment
The mode of the method for implementing the fluorine-containing lithium compound of preparation of the present invention is disclosed hereinafter, in detail.
In the present invention, the element M that contacts with LiF comprises the element that is selected from B, P, As, Sb, Bi, V, Nb and Ta, and its fluorochemical comprises AsF
3, SbF
3, SbF
5, BiF
3, VF
2, VF
4, VF
5, NbF
4, NbF
5, TaF
5Deng.Can unite and use two or more element M.
Because LiF and element M and/or its fluorochemical are in theory with 1: 1 molar ratio reaction, so these material feeding mol ratios are desirably 1: 1, the preferred feedstock mol ratio is worth near this.Yet the ratio of strictly adjusting and measuring 1: 1 is difficult.And, as industrial process, use the LiF that removes easily in the excessive slightly step in the back, be better than using excessive element M and/or its fluorochemical.Therefore, the mol ratio of LiF and element M and/or its fluorochemical is generally more than or equal to 1.0 and is less than or equal to 2.0, is preferably greater than 1.0 and be less than or equal to 1.5.
Because LiF and element M and/or its fluorochemical are solid, so consider that from their reactive behavior preferably its crystal is the particle that more segments, preferably its any particle has 100 μ m or littler mean particle size, and preferred 10 μ m or littler fine powder.Yet, because the problem that too thin powder can cause powder to scatter so preferred average particle size is 0.01 μ m or bigger, is preferably 0.1～10 μ m especially.Can be after granularity be adjusted to designated size in advance, use fluorochemical or the fluorochemical of element M and the mixture of element M of LiF and element M or LiF and element M, then mix, also can be by grinding these particles when mixing to adjust to this granularity.
Although also can distinguish charging LiF and element M in reactor, begin reaction then, preferably be pre-mixed LiF and element M, begin reaction then.As the method for mixing LiF and element M, perhaps as the method for the mixture of the fluorochemical of fluorochemical that mixes LiF and element M or element M and element M, mixing can be in single assembly, perhaps in a plurality of steps of separating, utilize the mixing machine of each mixing zone that is suitable for convection current, shearing and diffusion to carry out.
Particularly, can use the mixing tank of mortar as small quantities of particles.The preferable equipment that is used for the equipment of convection current mixing zone or can be used for all mixing zones of individual machine comprises: ribbon mixer, twin shell mixer, cone-type mixer etc.The preferable equipment that is used for the starting stage mixing zone of convection current comprises the air-jetting type mixing tank.The equipment of the mixing zone that is suitable for shearing and spreads is included in the mixing tank that has blade, roller etc. on each turning axle of the rotary-type and horizontal rotational shaft type of Z-axis.
React used fluorine gas (F
2) be gas at room temperature, and have extra high reactivity.Though the preferred F that does not have dilution that uses in reaction
2, use the F that it is the inert gasses dilution but also can use
2Can use rare gas (as helium, argon etc.), nitrogen, and carbon number is 4 or perfluoro alkane still less, as this rare gas element.In these rare gas elementes, the concentration of fluorine gas is generally 1% volume or more.Preferred 50% volume or more.Too low concentration of fluorine causes productivity to descend.
As the F that adds in element M and/or its fluorochemical
2Amount, must provide to form LiMF
xRequired theoretical amount at least or more preferably provides twice or more theoretical amount.Though consider the lot of F of charging from reactivity
2Not problem, but can produce the pressure and the unreacted F of device interior
2The problem of collection.Therefore, F
2Inlet amount be less than or equal to 100 times theoretical amount, preferably be less than or equal to 20 times theoretical amount.
Element M under LiF coexistence with F
2Reaction, the fluorochemical of element M under LiF coexistence with F
2Reaction, perhaps the fluorochemical of element M and element M under LiF coexistence with F
2Reaction, preferably undertaken by under 100 ℃ or higher temperature, heating.Yet as the feed of material and the mode of reaction, reaction can be with F
2Undertaken by heating after filling in the reactor that contains solid matter (being fluorochemical or LiF and the element M and the fluorochemical thereof of LiF and element M, LiF and element M), perhaps after the reactor of solid matter is equipped with in heating, by charging F
2Or make F
2Flow and carry out.Moreover, can also make F
2When flowing through reactor, provide solid material.And, can repeatedly carry out following step: use F
2Be full of contain solid matter reactor once, the heating specific time, then the cooling once, under reduced pressure or by means of rare gas element remove F
2, use F then
2Be full of reactor and heating once more.
Certainly, by suitably pursuing part feed reactants (as F
2Gas etc.), can improve reaction efficiency.
From improving the viewpoint of reactive behavior and security, introducing F
2Gas is before the reactor or after finishing reaction, and preferred reactor keeps high vacuum or makes reactor be full of rare gas element.And, in the reaction atmosphere during the preferred reaction (gas phase), except reacting formed intermediate, in fact only comprise F
2Gas and rare gas element.
Reactor can be batch system and/or flowing-type system.When using well-mixed solid matter, it is unnecessary stirring in reactor.Yet preferred the use is equipped with the reactor of horizontal or vertical turning axle, and has blade or roller on this turning axle, because reacting balance ground is carried out.
When product took out from reactor, in the reactor of batch system, can make in the following method: product was drawn from the bottom of reactor, scooped out from top, and drew from the reactor that fell; In the reactor of flowing-type system, can adopt the method for such extraction product, for example, when carrying out continuously, reaction takes out product by means of transport unit, screw feeder etc.
In a word, when taking out products therefrom, preferred product is placed in the inert gas atmosphere.And, when products therefrom has reactivity to the compound that brings from the open air such as water or oxygen, and when needing to keep degree of purity of production, need product is taken out from reactor under inert gas atmosphere and stores.
The present invention industrial be favourable because can obtain required fluorine-containing lithium compound, and need after with reactant supply response system, not take out the operation of any reaction intermediate, this is so-called one-pot synthesis.
Intermittent reaction is included in the pattern of reacting in the single reactor.
Because F
2Gas charges in the reactor or the reactor of flowing through, thus need to have high airtight quality under the described hereinafter reaction conditions of reactor, and can bear pressure and temperature.Yet, consider installation, not preferred designed reactor can bear more than the harsher condition of practical application.Therefore, preferred designed reactor adapts to selected reaction conditions just.
The material of reactor under the temperature and pressure of regulation, under the condition that lacks water, oxygen and other material except raw material, need bear successive F
2Gas.Particularly, the material of reactor comprises common anti-F
2Special steel, as stainless steel, Monel, Inconel etc.
Reaction pressure is preferably 0.1～100atm, and (0.01～10MPa), more preferably 0.5～10atm (0.05～1MPa).Temperature of reaction is preferably 100～1000 ℃, more preferably 200～500 ℃.
Reaction times changes with following factors: temperature, pressure, raw materials used amount, F
2Concentration, charge into F
2Method in multiplicity and make F
2The F of time per unit in the mobile method
2Flow, and other index, but be generally 1～500 hour.
Fluorine-containing lithium compound prepared in accordance with the present invention preferably includes LiPF
6, LiBF
4Deng.
Embodiment
Though method of the present invention specifically describes by embodiment hereinafter, and do not mean that and be limited to the following examples, as long as can prepare described material.
Embodiment 1
Under nitrogen atmosphere, utilize agate mortar, mix the LiF of 28.69mg (1.106mmol) and the red phosphorus of 34.23mg (1.105mmol).The gained mixture is put into the stainless steel pressure container that capacity is 21ml, and this container is pumped into high vacuum, and its atmosphere is replaced by Ar, once more container is found time, thus the oxygen in the eliminating atmosphere.
Then, after emptying pressurized vessel once more, to wherein charging into F
2Gas is to 4atm (0.4MPa) and sealing.Temperature is elevated to 300 ℃, and under this temperature, kept 10.5 hours.Then, leave standstill this pressurized vessel,, under reduced pressure remove unreacted F until reaching room temperature
2, and replace with Ar, afterwards, charge into F once more
2Gas is up to 4atm, heats similarly and keeps.Repeat this operation four times, then container is opened in Ar atmosphere, obtain the LiPF of 100.86mg
6(productive rate 96.08%).
Embodiment 2～5
By with embodiment 1 in identical mode react, different is, use the material shown in the table 1 to replace red phosphorus (mole number of the amount of substance that uses is identical with red phosphorus among the embodiment 1), the variation of reaction conditions is as shown in table 1, and then obtaining reaction product as shown in table 1, productive rate is as shown in table 1.
Table 1
| Embodiment | Raw material | Reaction conditions | Reaction product | Productive rate (%) | ||
| Temperature (℃) | Time (hour) | Multiplicity | ||||
| 1 | P | ??300 | 10.5 | 4 | LiPF 6 | 96.08 |
| 2 | As | ??460 | 30 | 4 | LiAsF 4 | 95.26 |
| 3 | Ta | ??380 | 18 | 4 | LiTaF 6 | 92.08 |
| 4 | TaF 5 | ??250 | 24 | 4 | LiTaF 6 | 98.86 |
| 5 | BiF 3 | ??150 | 48 | 4 | LiBiF 4 | 97.65 |
In in embodiment 1～5 any one, the reaction product of gained is differentiated with X-ray diffraction, confirms that product is the product of wishing separately, does not have the peak based on other compound.
Though the present invention at length and with reference to embodiment is illustrated that to one skilled in the art, obviously these modes can differently be changed or improve, and do not break away from the spirit and scope of the present invention.
The application is based on the Japanese patent application (application number is 2002-328548) of filing an application on November 12nd, 2002, and described content is introduced among the application as a reference.
Industrial applicibility
As above describe in detail, the method for the lithium compound that preparation according to the present invention is fluorine-containing contains the LiMF that the performance of battery is produced dysgenic impurity such as HF or its by product hardly
xCan make easily.
LiPF at the electrolytic solution that is used as lithium ion battery electrolyte solution
6In the preparation, method of the present invention is that a kind of performance that contains hardly battery that can prepare easily produces dysgenic impurity as method of electrolyte as described in HF or its by product, and the industrial applicibility of this method is very high.
Claims (6)
1. method for preparing fluorine-containing lithium compound, described fluorine-containing lithium compound is by formula LiMF
xShown in (M represents to be selected from the element of B, P, As, Sb, Bi, V, Nb and Ta, and x represents 4～6 number), it is characterized in that: under the situation that fluorine gas exists, LiF is contacted with element M.
2. method for preparing fluorine-containing lithium compound, described fluorine-containing lithium compound is by formula LiMF
xShown in (M represents to be selected from the element of B, P, As, Sb, Bi, V, Nb and Ta, and x represents 4～6 number), it is characterized in that: under the situation that fluorine gas exists, LiF and the fluorochemical of element M or the fluorochemical of element M and the mixture of element M are contacted.
3. according to the method for the fluorine-containing lithium compound of the preparation of claim 1, it is characterized in that: be pre-mixed LiF and element M, under the situation that fluorine gas exists, LiF contacted with element M then.
4. according to the method for the fluorine-containing lithium compound of each preparation in the claim 1 to 3, wherein, the temperature when under the situation that fluorine gas exists LiF being contacted with the fluorochemical of element M and/or element M is 100 ℃ or higher and 1000 ℃ or lower.
5. according to the method for the fluorine-containing lithium compound of each preparation in the claim 1 to 4, it is characterized in that: the catalytic reaction times of carrying out the fluorochemical of LiF and element M and/or element M under the situation that fluorine gas exists is 1～500 hour.
6. according to the method for the fluorine-containing lithium compound of each preparation in the claim 1 to 5, wherein said fluorine-containing lithium compound is for being selected from LiPF
6And LiBF
4Fluorine-containing lithium compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP328548/2002 | 2002-11-12 | ||
| JP2002328548 | 2002-11-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1711214A true CN1711214A (en) | 2005-12-21 |
| CN1304279C CN1304279C (en) | 2007-03-14 |
Family
ID=32310546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801029929A Expired - Fee Related CN1304279C (en) | 2002-11-12 | 2003-11-12 | Method for producing fluorine-containing lithium compound |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101068065B1 (en) |
| CN (1) | CN1304279C (en) |
| AU (1) | AU2003280748A1 (en) |
| WO (1) | WO2004043856A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102934276A (en) * | 2010-06-08 | 2013-02-13 | 中央硝子株式会社 | Method for producing electrolyte solution for lithium ion battery, and lithium ion battery using the electrolyte solution |
| CN110970604A (en) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Coated ternary cathode material, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003280748A1 (en) | 2002-11-12 | 2004-06-03 | Mitsubishi Chemical Corporation | Method for producing fluorine-containing lithium compound |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61151024A (en) * | 1984-12-25 | 1986-07-09 | Hashimoto Kasei Kogyo Kk | Production of high purity lithium fluoride complex salt |
| JPS6472901A (en) * | 1987-09-14 | 1989-03-17 | Central Glass Co Ltd | Production of lithium fluoride complex salt |
| JP4405007B2 (en) * | 1999-10-22 | 2010-01-27 | 関東電化工業株式会社 | Method for producing high purity lithium hexafluorophosphate |
| JP2001122605A (en) * | 1999-10-22 | 2001-05-08 | Kanto Denka Kogyo Co Ltd | Method for production of high purity lithium hexafluorophosphate |
| AU2003280748A1 (en) | 2002-11-12 | 2004-06-03 | Mitsubishi Chemical Corporation | Method for producing fluorine-containing lithium compound |
-
2003
- 2003-11-12 AU AU2003280748A patent/AU2003280748A1/en not_active Abandoned
- 2003-11-12 CN CNB2003801029929A patent/CN1304279C/en not_active Expired - Fee Related
- 2003-11-12 WO PCT/JP2003/014383 patent/WO2004043856A1/en active Application Filing
- 2003-11-12 KR KR1020057008441A patent/KR101068065B1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102934276A (en) * | 2010-06-08 | 2013-02-13 | 中央硝子株式会社 | Method for producing electrolyte solution for lithium ion battery, and lithium ion battery using the electrolyte solution |
| CN102934276B (en) * | 2010-06-08 | 2015-04-08 | 中央硝子株式会社 | Method for producing electrolyte solution for lithium ion battery, and lithium ion battery using the electrolyte solution |
| CN110970604A (en) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Coated ternary cathode material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003280748A8 (en) | 2004-06-03 |
| KR101068065B1 (en) | 2011-09-28 |
| CN1304279C (en) | 2007-03-14 |
| KR20050067436A (en) | 2005-07-01 |
| AU2003280748A1 (en) | 2004-06-03 |
| WO2004043856A1 (en) | 2004-05-27 |
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