WO2016103558A1 - リチウムリン系複合酸化物炭素複合体及びその製造方法並びに、電気化学デバイス及びリチウムイオン二次電池 - Google Patents
リチウムリン系複合酸化物炭素複合体及びその製造方法並びに、電気化学デバイス及びリチウムイオン二次電池 Download PDFInfo
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- WO2016103558A1 WO2016103558A1 PCT/JP2015/005670 JP2015005670W WO2016103558A1 WO 2016103558 A1 WO2016103558 A1 WO 2016103558A1 JP 2015005670 W JP2015005670 W JP 2015005670W WO 2016103558 A1 WO2016103558 A1 WO 2016103558A1
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- WIPO (PCT)
- Prior art keywords
- lithium
- carbon composite
- lithium phosphorus
- composite oxide
- negative electrode
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Definitions
- the present invention relates to a lithium phosphorus composite oxide carbon composite, a method for producing the same, an electrochemical device using the lithium phosphorus composite oxide carbon composite, and a lithium ion secondary battery.
- This secondary battery is not limited to a small electronic device, but is also considered to be applied to a large-sized electronic device represented by an automobile or the like, or an electric power storage system represented by a house.
- lithium ion secondary batteries are highly expected because they are small and easy to increase in capacity. This is because an energy density higher than that of a lead battery or a nickel cadmium battery can be obtained.
- the lithium ion secondary battery includes an electrolyte solution together with a positive electrode, a negative electrode, and a separator.
- the positive electrode and the negative electrode include a positive electrode active material and a negative electrode active material related to the charge / discharge reaction.
- lithium iron phosphate (LiFePO 4 ) having an olivine-type crystal structure has attracted attention as a positive electrode active material for lithium ion secondary batteries.
- This LiFePO 4 contains phosphorus (P) as a constituent element, and all oxygen is strongly covalently bonded to phosphorus. For this reason, even if it becomes high temperature, it does not release
- one lithium atom that can be inserted and removed by charging and discharging is contained per Fe atom, it has been studied as a positive electrode active material of a new lithium secondary battery that replaces lithium cobalt oxide.
- the lithium iron phosphate (LiFePO 4 ) carbon composite produced by the conventional method is a composite with a conductive carbon material, and there is a problem that the manufacturing process becomes complicated and the processing cost increases.
- a trivalent iron raw material is used, there is a problem that a reduction process is required and a sufficient charge / discharge capacity cannot be obtained.
- the lithium phosphorus complex oxide-carbon composite proposed in Patent Document 2 describes that it is synthesized from a trivalent FePO 4 .nH 2 O raw material, but this is still in terms of charge / discharge capacity. That's not enough.
- the lithium content of the positive electrode used for regeneration is non-uniform, A part of the inactive oxide layer is formed on the surface of the positive electrode during reproduction, and a sufficient charge / discharge capacity cannot be obtained.
- the regenerating method including the cooling step it is difficult to return to the original active material simply by re-firing in a state where lithium is unevenly put in and out, and high charge / discharge capacity is difficult to be reproduced.
- Patent Documents 7 and 8 Although the elements contained from the positive electrode active material can be recovered, it is difficult to regenerate the recovered material as it is to the positive electrode active material. That is, in the methods disclosed in Patent Documents 7 and 8, detailed processing conditions are not described, and the function (positive electrode capacity) as a positive electrode active material is recovered even if the undisclosed conditions are processed according to normal conditions. It was difficult to do.
- the present invention has been made in view of the above-mentioned problems, and when used as an active material for a positive electrode of an electrochemical device, a lithium phosphorus system that can obtain a high charge / discharge capacity even when a raw material containing trivalent is used.
- An object is to provide a composite oxide carbon composite and a method for producing the same.
- the present invention provides a lithium phosphorus composite oxide-carbon composite in which the surface of a lithium phosphorus composite oxide used as an active material for a positive electrode of an electrochemical device is coated with carbon, Fluorine ions eluted in an eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are in a mass ratio of 500 ppm to 15000 ppm with respect to the lithium phosphorus composite oxide carbon composite, and the lithium
- the composition of the phosphorus complex oxide is represented by the following general formula (1): Li 1 ⁇ x Fe 1 ⁇ z M z PO 4 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a 4) (1) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu, and Zn).
- a lithium phosphorus based composite oxide carbon composite is provided.
- lithium phosphorus complex oxide-carbon composite when used as an active material for the positive electrode of an electrochemical device, lithium ions can be smoothly inserted and removed, thereby stably supplying lithium ions appropriately. Therefore, the charge / discharge capacity can be increased.
- the lithium ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water is 500 ppm or more and 5000 ppm or less in a mass ratio with respect to the lithium phosphorus composite oxide carbon composite. It is preferable.
- the lithium ions eluted in the eluate when dispersed in ultrapure water are in the above range in terms of mass ratio to the lithium phosphorus composite oxide carbon composite, when used as an active material for the positive electrode of an electrochemical device
- the charge / discharge capacity can be increased more effectively.
- the mass ratio (the mass of fluorine ions / the mass of lithium ions) of lithium ions and fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide-carbon composite was dispersed with ultrapure water was 0. It is preferably 1 or more and 10 or less.
- the charge / discharge capacity is more reliably obtained when used as an active material for the positive electrode of an electrochemical device. Can be high.
- a peak corresponding to lithium phosphate is observed in the range where the value of 2 ⁇ is 20 ° or more and 25 ° or less by X-ray diffraction measurement.
- the lithium phosphorus complex oxide-carbon composite having such an X-ray diffraction pattern is used as an active material for the positive electrode of an electrochemical device, the charge / discharge capacity can be increased more reliably. It can use suitably for the positive electrode active material of a chemical device.
- the average particle size is preferably 0.5 ⁇ m or more and 30.0 ⁇ m or less.
- the charge / discharge capacity can be increased more effectively when used as an active material for the positive electrode of an electrochemical device.
- the BET specific surface area is preferably 5.0 m 2 / g or more and 50.0 m 2 / g or less.
- the charge / discharge capacity can be increased more effectively when used as an active material for the positive electrode of an electrochemical device.
- the composition of the present invention has the following general formula (1): Li 1 ⁇ x Fe 1 ⁇ z M z PO 4 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 4) (1) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu, and Zn).
- a method for producing a lithium phosphorus composite oxide-carbon composite whose surface is coated with carbon the composition of which is the following general formula (2): Li 1 ⁇ y Fe 1 ⁇ z M z PO 4 ⁇ b F b (x ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ b ⁇ 4) (2) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu, and Zn).
- the fluorine ions eluted into the eluate are 50 by mass ratio with respect to the lithium phosphorus composite oxide-carbon composite. ppm or more, to provide a method for manufacturing a lithium phosphorus compound oxide carbon complex, characterized in that it is an less 15000 ppm.
- the fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are in a predetermined range by mass ratio with respect to the lithium phosphorus composite oxide carbon composite.
- the lithium phosphorus complex oxide-carbon composite can be reliably produced.
- lithium is extracted from the lithium phosphorus composite oxide precursor electrochemically.
- Such a method can be suitably used as a method for extracting lithium.
- lithium is extracted electrochemically after the lithium phosphorus complex oxide precursor is molded with a thickness of 1.0 mm or more.
- Such a method can also be suitably used as a method for extracting lithium.
- the lithium compound preferably contains lithium hexafluorophosphate (LiPF 6 ).
- Fluorine can be contained in the lithium phosphorus composite oxide carbon composite by using a lithium compound containing lithium hexafluorophosphate as the lithium compound to be reacted with the lithium phosphorus composite oxide precursor.
- the lithium compound preferably contains lithium tetrafluoroborate (LiBF 4 ).
- Fluorine can be included in the lithium phosphorus composite oxide carbon composite by using a lithium compound containing lithium tetrafluoroborate as the lithium compound to be reacted with the lithium phosphorus composite oxide precursor.
- the step of reacting includes a step of firing, and in the step of firing, the firing temperature is preferably 500 ° C. or higher and 1000 ° C. or lower.
- a method of reacting the lithium phosphorus complex oxide precursor and the lithium compound a method of firing in the above temperature range can be suitably used.
- the reacting step includes a firing step, and the firing is performed in a nitrogen atmosphere.
- the reacting step includes a firing step, and the firing step is performed in an argon atmosphere.
- the present invention provides a negative electrode active material layer containing negative electrode active material particles having a charge and discharge efficiency of 80% or less when used as a negative electrode active material for an electrochemical device, and a negative electrode comprising a negative electrode current collector,
- a negative electrode active material layer containing negative electrode active material particles having a charge and discharge efficiency of 80% or less when used as a negative electrode active material for an electrochemical device and a negative electrode comprising a negative electrode current collector
- an electrochemical device comprising a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode comprising a positive electrode current collector.
- Such an electrochemical device can have a high charge / discharge capacity.
- the present invention also includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide having a composition formula represented by SiO x (0.5 ⁇ x ⁇ 1.6), and a negative electrode current collector.
- a negative electrode active material layer containing negative electrode active material particles containing silicon oxide having a composition formula represented by SiO x (0.5 ⁇ x ⁇ 1.6), and a negative electrode current collector.
- an electrochemical device comprising: a negative electrode, a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite, and a positive electrode comprising a positive electrode current collector.
- Such an electrochemical device can have a high charge / discharge capacity.
- the present invention also provides a negative electrode comprising a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of a lithium ion secondary battery, and a negative electrode current collector. And a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode comprising a positive electrode current collector.
- Such a lithium ion secondary battery can have a high charge / discharge capacity.
- the present invention also includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide having a composition formula represented by SiO x (0.5 ⁇ x ⁇ 1.6), and a negative electrode current collector. And a positive electrode comprising a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode current collector.
- Such a lithium ion secondary battery can have a high charge / discharge capacity.
- the lithium phosphorus composite oxide-carbon composite of the present invention when used as an active material for a positive electrode of an electrochemical device, lithium ions can be smoothly inserted and removed, thereby Since it can be supplied stably and appropriately, the charge / discharge capacity can be increased. Further, according to the method for producing a lithium phosphorus composite oxide-carbon composite of the present invention, fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are contained in the lithium phosphorus composite composite. A lithium phosphorus composite oxide carbon composite having a predetermined mass ratio with respect to the oxide carbon composite can be reliably produced. Furthermore, the electrochemical device of the present invention can have a high charge / discharge capacity. Moreover, if it is the lithium ion secondary battery of this invention, it can have a high charging / discharging capacity
- FIG. 3 is a diagram showing an X-ray diffraction pattern of a lithium phosphorus complex oxide-carbon composite of Example 1.
- the lithium iron phosphate (LiFePO 4 ) carbon composite produced by the conventional method is a composite with a conductive carbon material, which complicates the production process and increases the processing cost. there were.
- the present inventors have intensively studied a lithium-phosphorus-based composite oxide-carbon composite that can obtain a high charge / discharge capacity when used as a positive electrode active material for an electrochemical device even when a trivalent iron raw material is used. Repeated. As a result, the fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are in a mass ratio of 500 ppm or more and 15000 ppm or less with respect to the lithium phosphorus composite oxide carbon composite. It is found that a high charge / discharge capacity can be obtained when a lithium-phosphorous composite oxide-carbon composite is used as a positive electrode active material of an electrochemical device even if a trivalent iron raw material is used. It came to make.
- the lithium phosphorus composite oxide carbon composite of the present invention is a lithium phosphorus composite oxide carbon composite in which the surface of the lithium phosphorus composite oxide used for the active material of the positive electrode of the electrochemical device is coated with carbon.
- Fluorine ions eluted in the filtered eluate when dispersed with ultrapure water in a mass ratio with respect to the lithium phosphorus composite oxide carbon composite are 500 ppm or more and 15000 ppm or less, more preferably 1000 ppm or more and 15000 ppm or less, Preferably, it is 1500 ppm or more and 15000 ppm or less, and the composition of the lithium phosphorus composite oxide is represented by the following general formula (1): Li 1 ⁇ x Fe 1 ⁇ z M z PO 4 ⁇ a F a (0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a 4) (1) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu
- lithium phosphorus complex oxide-carbon composite when used as an active material for the positive electrode of an electrochemical device, lithium ions can be smoothly inserted and removed, thereby stably supplying lithium ions appropriately. Therefore, the charge / discharge capacity can be increased.
- the eluted fluorine ions are considered to be contained in the form of LiF on the composite surface. However, what is important in the present invention is that the amount when fluorine ions are eluted as described above is within the specified range. Fluorine may be dissolved in the base material.
- the lithium ions eluted in the filtered eluate when dispersed with ultrapure water are 500 ppm or more and 5000 ppm in mass ratio with respect to the lithium phosphorus composite oxide carbon composite. Or less, more preferably 600 ppm or more and 5000 ppm or less, and still more preferably 1000 ppm or more and 5000 ppm or less.
- the lithium ions eluted in the filtered eluate when dispersed with ultrapure water are in the above range in terms of mass ratio to the lithium phosphorus complex oxide-carbon composite, it was used as the active material for the positive electrode of the electrochemical device Sometimes, the charge / discharge capacity can be increased more effectively.
- the above lithium phosphorus complex oxide-carbon composite has a mass ratio of lithium ions to fluorine ions (mass of fluorine ions / mass of lithium ions) eluted in the filtered eluate when dispersed in ultrapure water. 0.1 or more and 10 or less, and more preferably 0.5 or more and 8 or less.
- the elution amount of fluorine ions can be controlled, for example, by controlling the amount of the electrolyte solution containing fluorine when the lithium phosphorus complex oxide precursor and the lithium compound are reacted. That is, when the fluorine is insufficient, the electrolytic solution is added and regenerated.
- the amount of fluorine ions eluted can be controlled by discharging the electrolytic solution by centrifugation or the like.
- the elution amount of lithium ions can be controlled by, for example, the amount of lithium source other than the electrolyte, the firing temperature, etc., if the elution amount of fluorine ions is determined.
- the lithium phosphorus composite oxide-carbon composite is preferably such that a peak corresponding to lithium phosphate is observed in the range of 2 ⁇ of 20 ° or more and 25 ° or less by X-ray diffraction measurement. Moreover, it is more preferable that the peak intensity corresponding to the obtained lithium phosphate is small.
- the lithium phosphorus complex oxide-carbon composite having such an X-ray diffraction pattern is used as an active material for the positive electrode of an electrochemical device, the charge / discharge capacity can be increased more reliably. If it can use suitably for the positive electrode active material of a chemical device and the peak intensity of the obtained lithium phosphate is as small as a detection limit, the reduction
- the average particle diameter (median diameter) of the lithium phosphorus complex oxide-carbon composite is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
- the standard of the average particle diameter is a volume standard.
- the charge / discharge capacity can be increased more effectively when used as an active material for the positive electrode of an electrochemical device. .
- BET specific surface area of the lithium-phosphorus compound oxide carbon composite material 5.0 m 2 / g or more is preferably from 50.0m 2 / g, 7.0m 2 / g or more, 50.0 m 2 / g or less is more preferable, and 10.0 m 2 / g or more and 50.0 m 2 / g or less is further preferable.
- the BET specific surface area means a surface area per unit mass determined by the BET method (a method in which gas particles such as nitrogen are adsorbed on solid particles and the surface area is measured from the adsorbed amount).
- the charge / discharge capacity can be increased more effectively when used as an active material for the positive electrode of an electrochemical device. .
- the content of the conductive carbon material is greater than 0% by mass, preferably 20% by mass or less, and 1.0% by mass or more and 20% by mass or less. More preferably, the content is 2% by mass or more and 20.0% by mass or less. This is because the charge / discharge capacity can be increased more reliably when used as an active material for the positive electrode of an electrochemical device.
- the lithium phosphorus complex oxide-carbon composite described above When the lithium phosphorus complex oxide-carbon composite described above is used as an active material for the positive electrode of an electrochemical device, the lithium ions can be smoothly inserted and removed, thereby stably stabilizing the lithium ions. Since it can supply, charge / discharge capacity can be made high.
- the method for producing a lithium phosphorus composite oxide-carbon composite of the present invention has a composition represented by the following general formula (1): Li 1 ⁇ x Fe 1 ⁇ z M z PO 4 ⁇ a F a ( ⁇ 0.1 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ a ⁇ 4) (1) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu, and Zn).
- a method for producing a lithium phosphorus composite oxide-carbon composite whose surface is coated with carbon the composition of which is the following general formula (2): Li 1 ⁇ y Fe 1 ⁇ z M z PO 4 ⁇ b F b (x ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ b ⁇ 4) (2) (Wherein M represents one or more metal elements selected from the group consisting of Mn, Ni, Co, V, Cr, Al, Nb, Ti, Cu, and Zn).
- the fluorine ions eluted in the eluate are in a mass ratio of 500 ppm or more to 15000 pp with respect to the lithium phosphorus composite oxide carbon composite. It is an below.
- x is more preferably 0 ⁇ x ⁇ 0.5, and further preferably 0 ⁇ x ⁇ 0.3.
- y is more preferably 0 ⁇ y ⁇ 0.8, and more preferably 0 ⁇ y ⁇ 0.6.
- z is more preferably 0 ⁇ z ⁇ 0.7, and further preferably 0 ⁇ z ⁇ 0.4.
- the fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are in a predetermined mass ratio with respect to the lithium phosphorus composite oxide carbon composite.
- lithium phosphorus composite oxide carbon composite precursor from which lithium is extracted contains trivalent iron and is difficult to regenerate, but if used as a raw material, the lithium phosphorus system used electrochemically The composite oxide can be regenerated, and a cost-competitive lithium phosphorus composite oxide-carbon composite can be produced.
- the amount of the lithium compound used can be reduced, so that the lithium phosphorus complex oxide-carbon composite can be produced at a low cost.
- the lithium phosphorus composite oxide precursor from which lithium is extracted is, for example, dissolved by using an organic solvent from the used electrode after charge and discharge. What was taken out, chemically extracted lithium, the state where lithium ions were scattered by baking at high temperature, the state after lithium was extracted from the powder or pellet by charging and discharging, etc. .
- the lithium phosphorus complex oxide precursor may be carbon-coated. If a lithium-phosphorus composite oxide precursor from which lithium is partially removed is used, a portion of lithium remains, so that a lithium-phosphorus composite oxide-carbon composite can be produced more than when a coprecipitate raw material is used.
- the lithium phosphorus complex oxide precursor Li 1-y Fe 1-z M z PO 4 -b F b is in a state returned to its original state by charge and discharge, Li 1 -y Fe 1 -z MzPO 4 -b F b You may reproduce
- regenerate from the state of (y 0).
- lithium is extracted from the lithium phosphorus composite oxide precursor electrochemically (specifically, by charge and discharge).
- Such a method can be suitably used as a method for extracting lithium. This is because lithium can be easily extracted.
- the lithium phosphorus composite oxide precursor is molded with a thickness of 1.0 mm or more, more preferably 5.0 mm or more, and then electrochemically. It is preferable that lithium is extracted.
- Such a method can be suitably used as a method for extracting lithium. This is because handling is good if the lithium phosphorus complex oxide precursor is molded with the above thickness.
- the lithium compound is, for example, lithium carbonate, lithium hydroxide, lithium oxide, lithium oxalate, lithium phosphate, lithium hexafluorophosphate, tetrafluoride.
- Lithium borate, etc. are mentioned, preferably lithium hydroxide, more preferably lithium hydroxide and lithium hexafluorophosphate, or a mixture of lithium hydroxide and lithium tetrafluoroborate, more preferably Is a mixture of lithium hydroxide and lithium hexafluorophosphate.
- Lithium hydroxide is particularly preferable because it is easily available industrially, has high reactivity, and is inexpensive. Further, it is a good lithium conductor contained as an electrolyte in a lithium hexafluorophosphate electrolyte and a lithium tetrafluoroborate electrolyte, and is an ideal lithium compound for obtaining an excellent charge / discharge capacity.
- the step of reacting includes a stage of firing, and in the stage of firing, the firing temperature is preferably 500 ° C. or higher and 1000 ° C. or lower, preferably 550 ° C. As described above, the temperature is more preferably 900 ° C. or less, and further preferably 550 ° C. or more and 800 ° C. or less.
- the firing time is preferably 1 hour or more and 50 hours or less, more preferably 2 hours or more and 15 hours or less, and further preferably 2 hours or more and 8 hours or less.
- the calcination temperature is preferably 150 ° C. or more and 450 ° C. or less, more preferably 200 ° C. or more and 300 ° C. or less, and the calcination time is It is preferably 30 minutes or longer and 5 hours or shorter, and more preferably 2 hours or longer and 5 hours or shorter.
- firing is preferably performed in an argon or nitrogen gas atmosphere.
- the argon or nitrogen gas atmosphere means an atmosphere containing 50% or more of argon or nitrogen gas.
- a mixed gas containing 1 to 10% of hydrogen is more preferable. This is to prevent oxidation of the lithium phosphorus composite oxide carbon composite.
- lithium-containing compound examples include a composite oxide composed of lithium and a transition metal element, or a phosphate compound having lithium and a transition metal element.
- lithium-containing compounds compounds having at least one of nickel, iron, manganese, and cobalt are preferable. These chemical formulas are represented by, for example, Li c M1O 2 or Li d M2PO 4 .
- M1 and M2 represent at least one or more transition metal elements, and the values of c and d vary depending on the battery charge / discharge state, but generally 0.05 ⁇ c ⁇ 1.1, 0.05 ⁇ d ⁇ 1.1.
- the composite oxide having lithium and a transition metal element include lithium cobalt composite oxide (Li c CoO 2 ) and lithium nickel composite oxide (Li c NiO 2 ).
- a method other than firing when the lithium phosphorus composite oxide precursor is mixed with a lithium compound and reacted, a method other than firing may be used. You may use together with another method. For example, when the reaction is performed, hydrothermal treatment may be performed, the number of firings may be increased, pellet molding may be performed, and firing may be performed.
- the fluorine ions eluted in the eluate in which the lithium phosphorus composite oxide carbon composite is dispersed with ultrapure water are converted into lithium phosphorus composite oxide. It is possible to reliably produce a lithium-phosphorus-based composite oxide-carbon composite that falls within the above-described predetermined range in terms of mass ratio with respect to the product carbon composite.
- the lithium phosphorus complex oxide-carbon composite described above can be used as a positive electrode active material for various electrochemical devices (for example, batteries, sensors, electrolytic cells, etc.).
- electrochemical device refers to a device including an electrode plate material through which an electric current flows, that is, a device that can extract electric energy in general, and includes an electrolytic cell, a primary battery, and a secondary battery. It is a concept that includes.
- the “secondary battery” is a concept including so-called storage batteries such as lithium ion secondary batteries, nickel hydride batteries, nickel cadmium batteries, and power storage elements such as electric double layer capacitors.
- the lithium composite oxide is particularly suitable as an electrode material for lithium ion secondary batteries and electrolytic cells.
- the shape of the electrolytic cell may be any shape as long as it contains an electrode plate material that allows current to flow.
- the shape of the lithium ion secondary battery can be applied to any of coins, buttons, sheets, cylinders, and square shapes.
- the use of the lithium ion secondary battery to which the lithium composite oxide of the present invention is applied is not particularly limited. For example, it can be used in notebook computers, laptop computers, pocket word processors, mobile phones, cordless phones, portable CDs, radios, etc. Examples include consumer electronic devices such as electronic devices, automobiles, electric vehicles, and game devices.
- the positive electrode active material layer may contain 50 to 100% by mass of the lithium phosphorus composite oxide-carbon composite of the present invention. Further, it contains any one or more of positive electrode active materials capable of occluding and releasing lithium ions, and may contain other materials such as binders, conductive assistants, and dispersants depending on the design. Good.
- the positive electrode has, for example, a positive electrode active material layer on both sides or one side of the current collector.
- the current collector may be formed of a conductive material such as aluminum, for example.
- the negative electrode active material is preferably any one of silicon oxides represented by the general formula SiO x (0.5 ⁇ x ⁇ 1.6), or a mixture of two or more thereof.
- the negative electrode active material layer contains the above negative electrode active material, and may contain other materials such as a binder, a conductive additive, and a dispersant depending on the design.
- the negative electrode has the same configuration as the positive electrode described above, and has, for example, a negative electrode active material layer on one side or both sides of a current collector. It is preferable that the negative electrode has a larger negative electrode charge capacity than the electric capacity (charge capacity as a battery) obtained from the lithium composite oxide active material agent. This is for suppressing the deposition of lithium metal on the negative electrode.
- binder for example, any one or more of a polymer material and a synthetic rubber can be used.
- the polymer material include polyvinylidene fluoride, polyimide, polyamideimide, aramid, polyacrylic acid, lithium polyacrylate, and carboxymethylcellulose.
- the synthetic rubber is, for example, styrene butadiene rubber, fluorine rubber, ethylene propylene diene, or the like.
- the lithium composite oxide conductive auxiliary agent and the negative electrode conductive auxiliary agent for example, any one or more of carbon materials such as carbon black, acetylene black, graphite, ketjen black, carbon nanotube, and carbon nanofiber can be used. .
- Electrode At least a part of the active material layer or the separator is impregnated with a liquid electrolyte (electrolytic solution).
- This electrolytic solution has an electrolyte salt dissolved in a solvent, and may contain other materials such as additives.
- the solvent include non-aqueous solvents.
- the non-aqueous solvent include the following materials. Ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2-dimethoxyethane or tetrahydrofuran.
- At least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is desirable. This is because better characteristics can be obtained. In this case, more advantageous characteristics can be obtained by combining a high viscosity solvent such as ethylene carbonate or propylene carbonate and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. This is because the dissociation property and ion mobility of the electrolyte salt are improved.
- the solvent contains at least one of a halogenated chain carbonate or a halogenated cyclic carbonate.
- a halogenated chain carbonate is a chain carbonate having halogen as a constituent element (at least one hydrogen is replaced by a halogen).
- the halogenated cyclic carbonate is a cyclic carbonate having halogen as a constituent element (at least one hydrogen is replaced by halogen).
- the kind of halogen is not particularly limited, but fluorine is more preferable. This is because a film having a higher quality than other halogens is formed. Further, the larger the number of halogens, the more desirable, because the resulting coating is more stable and the decomposition reaction of the electrolyte is reduced.
- the halogenated chain carbonate include fluoromethyl methyl carbonate and difluoromethyl methyl carbonate.
- halogenated cyclic carbonate include 4-fluoro-1,3-dioxolane-2-one and 4,5-difluoro-1,3-dioxolane-2-one.
- the solvent additive contains an unsaturated carbon bond cyclic carbonate. This is because a stable film is formed on the surface of the negative electrode during charging and discharging, and the decomposition reaction of the electrolyte can be suppressed.
- the unsaturated carbon bond cyclic ester carbonate include vinylene carbonate and vinyl ethylene carbonate.
- sultone cyclic sulfonate ester
- sultone include propane sultone and propene sultone.
- the solvent preferably contains an acid anhydride. This is because the chemical stability of the electrolytic solution is improved.
- the acid anhydride include propanedisulfonic acid anhydride.
- the electrolyte salt can contain, for example, any one or more of light metal salts such as lithium salts.
- the lithium salt include lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ).
- the content of the electrolyte salt is preferably 0.5 mol / kg or more and 2.5 mol / kg or less with respect to the solvent. This is because high ionic conductivity is obtained.
- the current collector of the electrode is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the configured lithium ion secondary battery and electrochemical device, but for example, stainless steel, nickel, aluminum, titanium, The surface of calcined carbon, aluminum or stainless steel is surface-treated with carbon, nickel, copper, titanium or silver.
- the negative electrode is made of copper, in addition to stainless steel, nickel, copper, titanium, aluminum, calcined carbon, etc. Or a surface of stainless steel treated with carbon, nickel, titanium, silver, or the like, or an Al—Cd alloy is used.
- the separator separates the positive electrode and the negative electrode and allows lithium ions to pass through while preventing current short-circuiting due to both-pole contact.
- This separator is formed of, for example, a porous film made of synthetic resin or ceramic, and may have a laminated structure in which two or more kinds of porous films are laminated.
- the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.
- the electrochemical device of the present invention comprises a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of an electrochemical device, and a negative electrode current collector, An electrochemical device having a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode made of a positive electrode current collector.
- the electrochemical device of the present invention includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6) and a negative electrode current collector.
- It may be an electrochemical device having a negative electrode composed of a body, and a positive electrode composed of a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode current collector. Note that the negative electrode and the positive electrode may not include a current collector.
- Such an electrochemical device can have a high charge / discharge capacity.
- the regenerated lithium phosphorus composite oxide-carbon composite tends to increase the powder resistance.
- the charge / discharge efficiency decreases. Therefore, the negative electrode active having a charge / discharge efficiency of 80% or less.
- the use of substance particles is preferable from the viewpoint of the balance between charge and discharge efficiency of the positive electrode and the negative electrode, and a stable charge and discharge current can be obtained.
- the lithium secondary battery of the present invention comprises a negative electrode active material layer containing negative electrode active material particles having a charge / discharge efficiency of 80% or less when used as a negative electrode active material of a lithium ion secondary battery, and a negative electrode current collector. And a positive electrode composed of a positive electrode active material layer containing the lithium phosphorus complex oxide-carbon composite and a positive electrode current collector.
- the lithium secondary battery of the present invention includes a negative electrode active material layer containing negative electrode active material particles containing silicon oxide represented by a composition formula of SiO x (0.5 ⁇ x ⁇ 1.6), and a negative electrode It may be a lithium ion secondary battery having a negative electrode comprising a current collector, and a positive electrode comprising a positive electrode active material layer containing the above lithium phosphorus complex oxide-carbon composite and a positive electrode current collector. Note that the negative electrode and the positive electrode may not include a current collector.
- Such a lithium secondary battery can have a high charge / discharge capacity.
- Example 1-4 Li 0.5 FePO 4 from which lithium was drawn to 50% at a constant current from pellet-shaped LiFePO 4 (with carbon coating) was dried while containing an electrolyte containing fluorine, and lightly ground into lithium hydroxide. (LiOH.H 2 O) was mixed so that the equivalent ratio of Li / Fe was 1.05 / 1.00. This mixture was calcined in a nitrogen-hydrogen mixed gas (hydrogen concentration: 3%), cooled, and finely pulverized.
- hydrogen concentration hydrogen concentration: 3%
- Example 1 a lithium phosphorus composite oxide-carbon composite having a composition of LiFePO 4 having a peak corresponding to lithium phosphate and having a surface coated with carbon was produced.
- the firing conditions were 650 ° C. and 8 hours in Example 1-2, 650 ° C. and 10 hours in Example 3, and 600 ° C. and 10 hours in Example 4.
- the powder obtained in Example 1 was subjected to X-ray diffraction measurement. The obtained X-ray diffraction pattern is shown in FIG. In the lithium phosphorus composite oxide-carbon composite obtained in Example 1 from FIG. 1, a peak corresponding to lithium phosphate (marked in FIG.
- Example 1 is marked) in the range of 2 ⁇ of 20 ° or more and 25 ° or less. It was confirmed that a peak was observed.
- Example 2-4 X-ray diffraction measurement was performed in the same manner as in Example 1, and it was confirmed that a peak corresponding to lithium phosphate was observed.
- Example 5-8 Li 0.5 FePO 4 from which lithium was extracted to 50% at a constant current from the pellet-molded LiFePO 4 was washed with DMC (dimethyl carbonate), dried by filtration, and lightly pulverized into lithium hydroxide (LiOH.H 2 O) and lithium hexafluoride (LiPF 6 , 5% of the total lithium added) are mixed so that the equivalent ratio of Li / Fe is 1.05 / 1.00, and sucrose (sucrose: C 12 H 22 O 11 ) was mixed. The mixture was baked in nitrogen gas, cooled and finely pulverized.
- DMC dimethyl carbonate
- LiPF 6 lithium hexafluoride
- Example 8 X-ray diffraction measurement was performed in the same manner as in Example 1, and it was confirmed that a peak corresponding to lithium phosphate was observed.
- Li 0.5 FePO 4 from which lithium was extracted to 50% at a constant current from pellet-molded LiFePO 4 was dried while containing an electrolyte containing fluorine, and lightly pulverized into lithium hydroxide (LiOH ⁇ H 2 O) and lithium tetrafluoroborate (LiBF 4 , 5% of the total lithium added) were mixed so that the equivalent ratio of Li / Fe was 1.05 / 1.00, and sucrose (sucrose: C 12 H 22 O 11 ) was mixed. The mixture was calcined in argon gas, cooled and finely pulverized.
- LiOH ⁇ H 2 O lithium hydroxide
- LiBF 4 lithium tetrafluoroborate
- Example 9-11 X-ray diffraction measurement was performed in the same manner as in Example 1, and it was confirmed that a peak corresponding to lithium phosphate was observed.
- Comparative Example 1-5 was also subjected to X-ray diffraction measurement in the same manner as in Example 1, but no peak corresponding to lithium phosphate was observed.
- the BET specific surface area of the lithium phosphorus complex oxide carbon composites of Example 1-11 and Comparative Example 1-5 was measured using Flowsorb 2300 (manufactured by Shimadzu Corporation). Table 1 shows the measurement results of the BET specific surface area.
- a positive electrode was produced using the lithium phosphorus complex oxide-carbon composites of Example 1-11 and Comparative Example 1-5 produced as described above.
- the produced lithium phosphorus composite oxide carbon composite 88% by mass, graphite powder 4.0% by mass, and polyvinylidene fluoride 8.0% by mass were mixed to obtain a positive electrode material, which was used as N-methyl-2-pyrrolidinone.
- a kneaded paste was prepared by dispersing in (hereinafter referred to as NMP). The kneaded paste was applied to an aluminum foil (current collector), dried, pressed and punched into a disk having a diameter of 15 mm to obtain a positive electrode plate.
- a SiO negative electrode was prepared.
- a raw material in which metallic silicon and silicon dioxide were mixed was placed in a reactor, deposited in a vacuum of 10 Pa, cooled sufficiently, and the deposit was taken out and pulverized by a ball mill. After adjusting the particle diameter, a carbon layer was obtained by performing thermal decomposition CVD as necessary.
- the prepared powder was subjected to bulk modification using an electrochemical method in a 1: 1 mixed solvent of propylene carbonate and ethylene carbonate (electrolyte salt 1.3 mol / kg). The obtained material is subjected to a drying treatment in a carbon dioxide atmosphere as necessary.
- the negative electrode active material particles, the precursor of the negative electrode binder, the conductive additive 1 (Ketjen black), and the conductive auxiliary agent 2 (acetylene black) are in a dry weight ratio of 80: 8: 10: 2.
- NMP was used as a solvent for the polyamic acid.
- the negative electrode mixture slurry was applied to the negative electrode current collector with a coating apparatus and then dried.
- baking was performed at 400 ° C. for 1 hour in a vacuum atmosphere. By this firing, a negative electrode binder (polyimide) was formed.
- a negative electrode plate was obtained by pressing and punching into a disk having a diameter of 16 mm.
- a non-aqueous electrolyte secondary coin battery was manufactured using each member such as the prepared positive electrode plate and negative electrode plate, separator, mounting bracket, external terminal, and electrolytic solution.
- the electrolytic solution one obtained by dissolving 1 mol of LiPF 6 in 1 liter of a 2: 7: 1 kneaded solution of ethylene carbonate, didiethyl carbonate, and fluoroethylene carbonate was used.
- the lithium phosphorus of Example 1-11 in which the fluorine ions eluted in the eluate dispersed with ultrapure water are in a mass ratio of 500 ppm or more and 15000 ppm or less with respect to the lithium phosphorus composite oxide-carbon composite.
- the fluorine ions eluted in the eluate dispersed in ultrapure water are in a mass ratio with respect to the lithium phosphorus composite oxide-carbon composite.
- a high discharge capacity is obtained as compared with a non-aqueous electrolyte secondary coin battery manufactured using the lithium phosphorus composite oxide-carbon composite of Comparative Example 1-5 of less than 500 ppm or greater than 15000 ppm.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
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Abstract
Description
Li1-xFe1-zMzPO4-aFa(-0.1≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるものであることを特徴とするリチウムリン系複合酸化物炭素複合体を提供する。
Li1-xFe1-zMzPO4-aFa(-0.1≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるリチウムリン系複合酸化物の表面が炭素被覆されたリチウムリン系複合酸化物炭素複合体を製造する方法であって、組成が下記一般式(2):
Li1-yFe1-zMzPO4-bFb(x<y<1、0≦z≦1、0≦b≦4)・・・(2)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるリチウムが引き抜かれたリチウムリン系複合酸化物前駆体をリチウム化合物と混合して、反応させる工程を有し、前記リチウムリン系複合酸化物前駆体として炭素被覆されたものを用いるか、又は、前記リチウムリン系複合酸化物前駆体若しくは前記リチウムリン系複合酸化物に対して炭素被覆する工程を有し、前記リチウムリン系複合酸化物前駆体、又は、前記リチウム化合物として、フッ素を含むものを用いることで、製造された前記リチウムリン系複合酸化物炭素複合体が、超純水で分散させた際に溶出液に溶出するフッ素イオンを前記リチウムリン系複合酸化物炭素複合体に対する質量比で500ppm以上、15000ppm以下とするものであることを特徴とするリチウムリン系複合酸化物炭素複合体の製造方法を提供する。
を有することを特徴とする電気化学デバイスを提供する。
を有することを特徴とするリチウムイオン二次電池を提供する。
Li1-xFe1-zMzPO4-aFa(0≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるものである。ここで、xは0≦x<0.5であることがより好ましく、0≦x<0.3であることがさらに好ましい。また、zは0<z<0.7であることがより好ましく、0<z<0.4であることがさらに好ましい。
Li1-xFe1-zMzPO4-aFa(-0.1≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるリチウムリン系複合酸化物の表面が炭素被覆されたリチウムリン系複合酸化物炭素複合体を製造する方法であって、組成が下記一般式(2):
Li1-yFe1-zMzPO4-bFb(x<y<1、0≦z≦1、0≦b≦4)・・・(2)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)で表わされるリチウムが引き抜かれたリチウムリン系複合酸化物前駆体をリチウム化合物と混合して、反応させる工程を有し、リチウムリン系複合酸化物前駆体として炭素被覆されたものを用いるか、又は、リチウムリン系複合酸化物前駆体若しくはリチウムリン系複合酸化物に対して炭素被覆する工程を有し、リチウムリン系複合酸化物前駆体、又は、リチウム化合物として、フッ素を含むものを用いることで、製造されたリチウムリン系複合酸化物炭素複合体が、超純水で分散させた際に溶出液に溶出するフッ素イオンをリチウムリン系複合酸化物炭素複合体に対する質量比で500ppm以上、15000ppm以下とするものである。ここで、xは0≦x<0.5であることがより好ましく、0≦x<0.3であることがさらに好ましい。また、yは0<y<0.8がより好ましく、0<y<0.6がさらに好ましい。さらに、zは0<z<0.7であることがより好ましく、0<z<0.4であることがさらに好ましい。
正極活物質層は、本発明のリチウムリン系複合酸化物炭素複合体を50~100質量%含むものとすることができる。また、リチウムイオンの吸蔵放出可能な正極活物質のいずれか1種又は2種以上を含んでおり、設計に応じて結着剤、導電助剤、分散剤などの他の材料を含んでいてもよい。
正極は、例えば、集電体の両面または片面に正極活物質層を有している。集電体は、例えば、アルミニウムなどの導電性材により形成されているものでも良い。
負極活物質は、一般式SiOx(0.5≦x<1.6)で表される酸化珪素のいずれか、又はこれらのうち2以上の混合物とすることが好ましい。負極活物質層は、上記の負極活物質を含んでおり、設計に応じて結着剤、導電助剤、分散剤などの他の材料を含んでいてもよい。
負極は、上記した正極と同様の構成を有し、例えば、集電体の片面もしくは両面に負極活物質層を有している。この負極は、リチウム複合酸化物活物質剤から得られる電気容量(電池として充電容量)に対して、負極充電容量が大きくなる事が好ましい。負極上でのリチウム金属の析出を抑制するためである。
結着剤として、例えば高分子材料、合成ゴムなどのいずれか1種類以上を用いることができる。高分子材料は、例えば、ポリフッ化ビニリデン、ポリイミド、ポリアミドイミド、アラミド、ポリアクリル酸、あるいはポリアクリル酸リチウム、カルボキシメチルセルロース等である。合成ゴムは、例えば、スチレンブタジエン系ゴム、フッ素系ゴム、エチレンプロピレンジエン等である。
リチウム複合酸化物導電助剤、負極導電助剤としては、例えば、カーボンブラック、アセチレンブラック、黒鉛、ケチェンブラック、カーボンナノチューブ、カーボンナノファイバーなどの炭素材料のいずれか1種以上を用いることができる。
活物質層の少なくとも一部、またはセパレータには液状の電解質(電解液)が含浸されている。この電解液は、溶媒中に電解質塩が溶解されており、添加剤など他の材料を含んでいても良い。溶媒は、例えば非水溶媒が挙げられる。非水溶媒として、例えば次の材料が挙げられる。炭酸エチレン、炭酸プロピレン、炭酸ブチレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチル、炭酸メチルプロピル、1,2-ジメトキシエタンあるいはテトラヒドロフランである。その中でも、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチルのうちの少なくとも1種以上が望ましい。より良い特性が得られるからである。またこの場合、炭酸エチレン、炭酸プロピレンなどの高粘度溶媒と、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチルなどの低粘度溶媒を組み合わせるとより優位な特性を得ることができる。電解質塩の解離性やイオン移動度が向上するためである。
電極の集電体は、構成されたリチウムイオン二次電池、電気化学デバイスにおいて化学変化を起こさない電子伝導体であれば特に制限されるものではないが、例えばステンレス鋼、ニッケル、アルミニウム、チタン、焼成炭素、アルミニウムやステンレス鋼の表面をカーボン、ニッケル、銅、チタンまたは銀で表面処理したものが用いられ、負極にはステンレス鋼、ニッケル、銅、チタン、アルミニウム、焼成炭素などの他に、銅やステンレス鋼の表面をカーボン、ニッケル、チタンまたは銀などで処理したもの、Al-Cd合金などが用いられる。
セパレータは、正極と負極を隔離し、両極接触に伴う電流短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータは、例えば、合成樹脂、あるいはセラミックからなる多孔質膜により形成されており、2種以上の多孔質膜が積層された積層構造を有しても良い。合成樹脂として、例えば、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレンなどが挙げられる。
ペレット成型したLiFePO4(炭素被覆あり)から、一定電流で50%までリチウムを引き抜いたLi0.5FePO4をフッ素を含む電解液を含んだまま、乾燥し、軽く粉砕した粉末に水酸化リチウム(LiOH・H2O)をLi/Feの当量比が1.05/1.00になるようにして混合した。この混合物を窒素-水素混合ガス(水素濃度3%)中で焼成した後、冷却し、細かく粉砕した。次いで、目開き75μmの篩で分級し、リン酸リチウムに相当するピークを有するLiFePO4の組成をもち、表面が炭素で被覆されたリチウムリン系複合酸化物炭素複合体を製造した。ただし、焼成条件は、実施例1-2では650℃、8時間、実施例3では650℃、10時間、実施例4では600℃、10時間とした。実施例1で得られた粉体についてX線回折測定を行った。得られたX線回折パターンを図1に示す。図1から実施例1で得られたリチウムリン系複合酸化物炭素複合体において、2θの値が20°以上、25°以下の範囲にリン酸リチウムに相当するピーク(図1中の印を付けたピーク)が見られることが確認された。実施例2-4についても実施例1と同様にしてX線回折測定を行い、リン酸リチウムに相当するピークが見られることが確認された。
ペレット成型したLiFePO4から、一定電流で50%までリチウムを引き抜いたLi0.5FePO4をDMC(ジメチルカーボネート)で洗浄して、濾過乾燥し、軽く粉砕した粉末に水酸化リチウム(LiOH・H2O)と六フッ化リチウム(LiPF6、添加した総リチウムの5%)をLi/Feの当量比が1.05/1.00になるようにして混合し、さらにスクロース(ショ糖:C12H22O11)を混合した。この混合物を窒素ガス中で焼成した後、冷却し、細かく粉砕した。次いで、目開き75μmの篩で分級し、リン酸リチウムに相当するピークを有するLiFePO4の組成をもち、表面が炭素で被覆されたリチウムリン系複合酸化物炭素複合体を製造した。ただし、焼成条件は、実施例5では700℃、3時間、実施例6では580℃、4時間、実施例7では750℃、4時間、実施例8では550℃、5時間とした。実施例5-8についても実施例1と同様にしてX線回折測定を行い、リン酸リチウムに相当するピークが見られることが確認された。
ペレット成型したLiFePO4から、一定電流で50%までリチウムを引き抜いたLi0.5FePO4をフッ素を含む電解液を含んだまま、乾燥し、軽く粉砕した粉末に水酸化リチウム(LiOH・H2O)と四フッ化ホウ酸リチウム(LiBF4、添加した総リチウムの5%)をLi/Feの当量比が1.05/1.00になるようにして混合し、さらにスクロース(ショ糖:C12H22O11)を混合した。この混合物をアルゴンガス中で焼成した後、冷却し、細かく粉砕した。次いで、目開き75μmの篩で分級し、リン酸リチウムに相当するピークを有するLiFePO4の組成をもち、表面が炭素で被覆されたリチウムリン系複合酸化物炭素複合体を製造した。ただし、焼成条件は、実施例9では780℃、4時間、実施例10では650℃、4時間、実施例11では650℃、4時間とした。実施例9-11についても実施例1と同様にしてX線回折測定を行い、リン酸リチウムに相当するピークが見られることが確認された。
ペレット成型したLiFePO4から、一定電流で50%までリチウムを引き抜いたLi0.5FePO4をフッ素を含む電解液を含んだまま、乾燥し、軽く粉砕した粉末に水酸化リチウム(LiOH・H2O)をLi/Feの当量比が1.05/1.00になるようにして混合した。この混合物をアルゴンガス中で焼成した後、冷却し、細かく粉砕した。次いで、目開き75μmの篩で分級し、リン酸リチウムに相当するピークを有するLiFePO4の組成をもつリチウムリン系複合酸化物炭素複合体を製造した。ただし、焼成条件は、比較例1では500℃、10時間、比較例2では900℃、10時間、比較例3-5では650℃、5時間とした。比較例1-5についても実施例1と同様にしてX線回折測定を行ったが、リン酸リチウムに相当するピークは見られなかった。
実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体の粒度分布の測定は、イオン交換水を分散媒とし、マイクロトラックMK-II(SRA)(LEED&NORTHRUP、レーザー散乱光検出型)を用いて行った。
なお、粒度分布の測定における分散剤、環流量、超音波出力を以下に示す。
分散剤 :10%ヘキサメタリン酸ソーダ水溶液2ml
環流量 :40ml/sec
超音波出力 :40W 60秒
平均粒子径の測定結果を表1に示す。
実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体のBET比表面積の測定は、フローソーブ2300型(島津製作所製)を用いて行った。
BET比表面積の測定結果を表1に示す。
実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体を超純水で分散させた溶出液に溶出するフッ素イオンの質量をICP法(高周波誘導結合プラズマ法)により測定し、リチウムリン系複合酸化物炭素複合体に対する質量比を算出した。得られた質量比を表1に示す。
実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体を超純水で分散させた溶出液に溶出するリチウムイオンの質量を測定し、リチウムリン系複合酸化物炭素複合体に対する質量比をICP法(高周波誘導結合プラズマ法)により算出した。得られた質量比を表1に示す。また、このときの溶出フッ素イオンと溶出リチウムイオンの質量比(フッ素イオンの質量/リチウムイオンの質量)も表1に示す。
実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体について、含有炭素量を、炭素分析装置(HORIBA EMIA-110)を用いて測定した。
測定結果を表1に示す。
(正極の作製)
上記のように製造した実施例1-11、比較例1-5のリチウムリン系複合酸化物炭素複合体を用いて、正極を作製した。製造したリチウムリン系複合酸化物炭素複合体88質量%、黒鉛粉末4.0質量%、及び、ポリフッ化ビニリデン8.0質量%を混合して正極材とし、これをN-メチル-2-ピロリジノン(以下、NMPと称する)に分散させて混練ペーストを調製した。該混練ペーストをアルミ箔(集電体)に塗布したのち乾燥し、プレスして直径15mmの円盤に打ち抜いて正極板を得た。
次にSiO負極を作成した。SiO負極は金属ケイ素と二酸化ケイ素を混合した原料を反応炉へ設置し、10Paの真空度中で堆積し、十分に冷却した後、堆積物を取出しボールミルで粉砕した。粒径を調整した後、必要に応じて熱分解CVDを行うことで炭素層を得た。作成した粉末はプロピレンカーボネート及びエチレンカーボネートの1:1混合溶媒(電解質塩1.3mol/kg)中で電気化学法を用いバルク改質を行った。得られた材料は必要に応じて炭酸雰囲気下で乾燥処理を行っている。続いて、負極活物質粒子と、負極結着剤の前駆体と、導電助剤1(ケッチェンブラック)と、導電助剤2(アセチレンブラック)とを80:8:10:2の乾燥重量比で混合して負極剤とし、NMPで希釈してペースト状の負極合剤スラリーとした。この場合には、ポリアミック酸の溶媒としてNMPを用いた。続いて、コーティング装置で負極集電体に負極合剤スラリーを塗布してから乾燥させた。この負極集電体としては、電解銅箔(厚さ=15μm)を用いた。最後に、真空雰囲気中で400℃、1時間焼成した。この焼成により、負極結着剤(ポリイミド)が形成された。プレスして直径16mmの円盤に打ち抜いて負極板を得た。
作製した正極板及び負極版、セパレータ、取り付け金具、外部端子、及び、電解液等の各部材を使用して非水電解質二次コイン電池を製作した。このうち、電解液には、エチレンカーボネートとジジエチルカーボネートとフルオロエチレンカーボネイトの2:7:1 混練液1リットルにLiPF61モルを溶解したものを使用した。
上記のようにして作製したコイン型リチウムイオン二次電池を0.5Cに相当する電流で定電流定電圧で4.00Vまで5時間充電し、次いで0.1Cに相当する電流で2.5Vまで放電する充放電試験を行い、正極初回放電容量(mAh/g)を測定した。測定結果を表1に示す。
Claims (18)
- 電気化学デバイスの正極の活物質に用いられる、リチウムリン系複合酸化物の表面が炭素被覆されたリチウムリン系複合酸化物炭素複合体であって、
前記リチウムリン系複合酸化物炭素複合体を超純水で分散させた溶出液に溶出するフッ素イオンが前記リチウムリン系複合酸化物炭素複合体に対する質量比で500ppm以上、15000ppm以下であり、
前記リチウムリン系複合酸化物の組成が下記一般式(1):
Li1-xFe1-zMzPO4-aFa(-0.1≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)
で表わされるものであることを特徴とするリチウムリン系複合酸化物炭素複合体。 - 前記リチウムリン系複合酸化物炭素複合体を超純水で分散させた溶出液に溶出するリチウムイオンが前記リチウムリン系複合酸化物炭素複合体に対する質量比で500ppm以上、5000ppm以下であることを特徴とする請求項1に記載のリチウムリン系複合酸化物炭素複合体。
- 前記リチウムリン系複合酸化物炭素複合体を超純水で分散させた溶出液に溶出するリチウムイオンと前記フッ素イオンとの質量比(フッ素イオンの質量/リチウムイオンの質量)が、0.1以上、10以下であることを特徴とする請求項1又は請求項2に記載のリチウムリン系複合酸化物炭素複合体。
- X線回折測定により、2θの値が20°以上、25°以下の範囲にリン酸リチウムに相当するピークが見られることを特徴とする請求項1から請求項3のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体。
- 平均粒子径が、0.5μm以上、30.0μm以下であることを特徴とする請求項1から請求項4のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体。
- BET比表面積が5.0m2/g以上、50.0m2/g以下であることを特徴とする請求項1から請求項5いずれか1項に記載のリチウムリン系複合酸化物炭素複合体。
- 組成が下記一般式(1):
Li1-xFe1-zMzPO4-aFa(-0.1≦x<1、0≦z≦1、0≦a≦4)・・・(1)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)
で表わされるリチウムリン系複合酸化物の表面が炭素被覆されたリチウムリン系複合酸化物炭素複合体を製造する方法であって、
組成が下記一般式(2):
Li1-yFe1-zMzPO4-bFb(x<y<1、0≦z≦1、0≦b≦4)・・・(2)
(式中、MはMn、Ni、Co、V、Cr、Al、Nb、Ti、Cu、Znの群から選ばれる1種以上の金属元素を示す。)
で表わされるリチウムが引き抜かれたリチウムリン系複合酸化物前駆体をリチウム化合物と混合して、反応させる工程を有し、
前記リチウムリン系複合酸化物前駆体として炭素被覆されたものを用いるか、又は、前記リチウムリン系複合酸化物前駆体若しくは前記リチウムリン系複合酸化物に対して炭素被覆する工程を有し、
前記リチウムリン系複合酸化物前駆体、又は、前記リチウム化合物として、フッ素を含むものを用いることで、製造された前記リチウムリン系複合酸化物炭素複合体が、超純水で分散させた際に溶出液に溶出するフッ素イオンを前記リチウムリン系複合酸化物炭素複合体に対する質量比で500ppm以上、15000ppm以下とするものであることを特徴とするリチウムリン系複合酸化物炭素複合体の製造方法。 - 前記リチウムリン系複合酸化物前駆体が、電気化学的にリチウムが引き抜かれていることを特徴とする請求項7に記載のリチウムリン系複合酸化物炭素複合体の製造方法。
- 前記リチウムリン系複合酸化物前駆体が、厚みが1.0mm以上で成型されてから、電気化学的にリチウムが引き抜かれていることを特徴とする請求項7に記載のリチウムリン系複合酸化物炭素複合体の製造方法。
- 前記リチウム化合物は、六フッ化リン酸リチウム(LiPF6)を含んでいることを特徴とする請求項7から請求項9のいずれか一項に記載のリチウムリン系複合酸化物炭素複合体の製造方法。
- 前記リチウム化合物は、四フッ化ホウ酸リチウム(LiBF4)を含んでいることを特徴とする請求項7から請求項10のいずれか一項に記載のリチウムリン系複合酸化物炭素複合体の製造方法。
- 前記反応させる工程が、焼成する段階を含み、
前記焼成する段階において、焼成温度が500℃以上、1000℃以下であることを特徴とする請求項7から請求項11のいずれか一項に記載のリチウムリン系複合酸化物炭素複合体の製造方法。 - 前記反応させる工程が、焼成する段階を含み、
前記焼成する段階において、窒素雰囲気で焼成することを特徴とする請求項7から請求項12のいずれか一項に記載のリチウムリン系複合酸化物炭素複合体の製造方法。 - 前記反応させる工程が、焼成する段階を含み、
前記焼成する段階において、アルゴン雰囲気で焼成することを特徴とする請求項7から請求項12のいずれか一項に記載のリチウムリン系複合酸化物炭素複合体の製造方法。 - 電気化学デバイスの負極活物質として用いたときに充放電効率が80%以下である負極活物質粒子を含有する負極活物質層と、負極集電体とからなる負極と、
請求項1から請求項6のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体を含む正極活物質層と、正極集電体とからなる正極と
を有することを特徴とする電気化学デバイス。 - 組成式がSiOx(0.5≦x<1.6)で表される酸化珪素を含有する負極活物質粒子を含有する負極活物質層と、負極集電体とからなる負極と、
請求項1から請求項6のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体を含む正極活物質層と、正極集電体とからなる正極と
を有することを特徴とする電気化学デバイス。 - リチウムイオン二次電池の負極活物質として用いたときに充放電効率が80%以下である負極活物質粒子を含有する負極活物質層と、負極集電体とからなる負極と、
請求項1から請求項6のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体を含む正極活物質層と、正極集電体とからなる正極と
を有することを特徴とするリチウムイオン二次電池。 - 組成式がSiOx(0.5≦x<1.6)で表される酸化珪素を含有する負極活物質粒子を含有する負極活物質層と、負極集電体とからなる負極と、
請求項1から請求項6のいずれか1項に記載のリチウムリン系複合酸化物炭素複合体を含む正極活物質層と、正極集電体とからなる正極と
を有することを特徴とするリチウムイオン二次電池。
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