WO2013031331A1 - ナトリウム電池用正極活物質及びその製造方法 - Google Patents
ナトリウム電池用正極活物質及びその製造方法 Download PDFInfo
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- WO2013031331A1 WO2013031331A1 PCT/JP2012/065096 JP2012065096W WO2013031331A1 WO 2013031331 A1 WO2013031331 A1 WO 2013031331A1 JP 2012065096 W JP2012065096 W JP 2012065096W WO 2013031331 A1 WO2013031331 A1 WO 2013031331A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention relates to the positive electrode active material for sodium batteries, and its manufacturing method.
- a lithium metal composite oxide having a layered structure such as lithium nickelate or lithium cobaltate is generally used as a positive electrode active material, and lithium ion can be occluded / released as a negative electrode active material.
- Carbon materials, lithium metals, lithium alloys and the like are used.
- an electrolyte solution in which a lithium salt is dissolved, a solid electrolyte containing lithium, or the like is used.
- Lithium batteries are excellent in energy density and output as described above. On the other hand, the price of lithium has increased along with the expansion of demand for lithium batteries, and the amount of lithium reserves has been limited. It has become a bottleneck in the process.
- Patent Document 1 describes Ma x Mb y P 2 O 7 (Ma represents Na, Li, Ca, or Mg, Mb represents a transition metal that is tetravalent or more and stably exists, and 0 ⁇ x ⁇ 4. , 0.5 ⁇ y ⁇ 3 and 6 ⁇ z ⁇ 14).
- MoP 2 O 7 MoP 2 O 7 that is actually manufactured and evaluated in the examples.
- Patent Document 1 when MoP 2 O 7 produced and evaluated in the example of Patent Document 1 is used as the positive electrode active material of a sodium battery, there is a problem that the operating potential is low. Further, as described in Non-Patent Documents 1 to 4, currently common positive electrode active materials for sodium batteries have a high operating potential of about 3.5V.
- Patent Document 2 describes Li 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) as an active material for lithium batteries. 5 describes that LiCoO 2 exhibits a potential of about 4V.
- Patent Document 1 since MoP 2 O 7 actually produced and evaluated in Patent Document 1 does not contain Na, when used as a positive electrode active material of a sodium battery, the operation of the sodium battery is caused by insertion of Na ions (discharge). Reaction). Therefore, it is necessary to use an active material containing Na in advance as the negative electrode active material to be combined.
- a Na-containing negative electrode active material that operates in a low potential region and can secure a sufficient electromotive force has not been reported at present, and there is a problem that it is difficult to put into practical use.
- the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a positive electrode active material for sodium batteries that has a high operating potential and can be charged and discharged at a high potential, and a method for producing the same. .
- the positive electrode active material for sodium batteries of the present invention is represented by the following general formula (1).
- General formula (1) Na x M y (AO 4) z (P 2 O 7) w
- M is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn
- A is Al, Si, P, S
- It is at least one selected from the group consisting of Ti, V and W, x satisfies 4 ⁇ x ⁇ 2, y satisfies 4 ⁇ y ⁇ 1, z satisfies 4 ⁇ z ⁇ 0, and w is 1 ⁇ w ⁇ 0 is satisfied, and at least one of z and w is 1 or more.
- the positive electrode active material for sodium batteries of the present invention has a high operating potential and realizes a high energy density of sodium batteries.
- the M is preferably divalent before charging. It is because it becomes possible to operate at a high potential by being in a highly oxidized state of 3 or more during charging.
- the positive electrode active material for a sodium battery of the present invention preferably has a crystal structure belonging to the space group Pn2 1 a.
- all of the Na ions in the crystal structure are arranged in any one of the a-axis, b-axis, and c-axis, which is very advantageous for Na ion conduction. This is because.
- the M is at least one selected from the group consisting of Mn, Co, and Ni, and a part thereof , Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, which may be substituted with at least one selected from the group consisting of M and the like.
- the positive electrode active material for a sodium battery in such a form easily takes a crystal structure belonging to the space group Pn2 1 a and is excellent in Na ion conductivity.
- M is Ni
- a part of Ni is Ti, V, Cr, Mn, Fe, Co.
- Cu and Zn may be substituted with at least one selected from the group consisting of.
- the A is at least one selected from the group consisting of Si, P and S, and a part thereof Is selected from the group consisting of Al, Si, P, S, Ti, V, and W, and may be substituted with at least one different from A.
- the positive electrode active material for a sodium battery in such a form easily takes a crystal structure belonging to the space group Pn2 1 a and is excellent in Na ion conductivity.
- A is P, and a part of P is Al, Si, S, Ti, V and W. The thing which may be substituted by at least 1 sort (s) chosen from the group which consists of is mentioned.
- the positive electrode active material for sodium batteries of the present invention for example, a compound represented by the general formula Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ), a general formula Na 4 Mn 3 (PO 4 ) 2 compound represented by (P 2 O 7), the general formula Na 4 Co 3 (PO 4) 2 compound represented by (P 2 O 7), the general formula Na 4 Co (3-a) Mn a (PO 4) 2 A compound represented by (P 2 O 7 ) (a satisfies 0.3 ⁇ a ⁇ 0.8), the general formula Na 4 Co (3-bc) Mn b Ni c (PO 4 ) 2 (P 2 O 7 ) (b satisfies 0.3 ⁇ b ⁇ 1.0, and c satisfies 0.3 ⁇ c ⁇ 1.0).
- the method for producing a positive electrode active material for a sodium battery of the present invention is a method for producing the positive electrode active material for a sodium battery of the present invention, A calcining step of calcining a raw material mixture containing at least an Na-containing compound, an M-containing compound containing M, an A-containing compound containing A, and a P-containing compound at 150 to 500 ° C. in an air atmosphere; After the preliminary firing, a final firing step of firing the obtained temporary fired product at 500 to 800 ° C. in an air atmosphere; It is characterized by including.
- the manufacturing method of the positive electrode active material for sodium batteries of this invention includes the grinding
- the present invention it is possible to provide a positive electrode active material for a sodium battery that has a high operating potential and can be charged and discharged at a high potential. Therefore, by using the positive electrode active material for sodium battery of the present invention, it is possible to increase the energy density of the sodium battery.
- FIG. 3 is an XRD pattern of a positive electrode active material synthesized in Example 1.
- FIG. 3 The result of the CV measurement which used Na metal as a counter electrode about the positive electrode using the positive electrode active material synthesize
- 3 is an XRD pattern of a positive electrode active material synthesized in Example 2.
- 3 shows the charge / discharge characteristics (relationship between capacity density and potential) of a positive electrode using the positive electrode active material synthesized in Example 2.
- 3 is an XRD pattern of a positive electrode active material synthesized in Example 3.
- FIG. 3 shows the charge / discharge characteristics (relationship between capacity density and potential) of a positive electrode using the positive electrode active material synthesized in Example 3.
- the cycle characteristics (relationship between the number of cycles and charge / discharge capacity density) of the positive electrode using the positive electrode active material synthesized in Example 3 are shown.
- 3 shows the charge / discharge characteristics (relationship between capacity density and potential) of a positive electrode using the positive electrode active material synthesized in Example 3.
- 3 shows the results of evaluation of the charge / discharge characteristics of the positive electrode using the positive electrode active material synthesized in Examples 4 to 8.
- 3 shows discharge curves of a positive electrode using the positive electrode active material synthesized in Examples 4 to 8. The cycle characteristics of the positive electrode using the positive electrode active material synthesized in Examples 4 to 8 are shown.
- 3 shows the results of evaluation of the charge / discharge characteristics of the positive electrode using the positive electrode active material synthesized in Examples 9 to 12.
- the positive electrode active material for a sodium battery of the present invention (hereinafter sometimes simply referred to as a positive electrode active material) and the production method thereof will be described in detail.
- the positive electrode active material for sodium batteries of the present invention is represented by the following general formula (1).
- General formula (1) Na x M y (AO 4) z (P 2 O 7) w
- M is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn
- A is Al, Si, P, S
- It is at least one selected from the group consisting of Ti, V and W, x satisfies 4 ⁇ x ⁇ 2, y satisfies 4 ⁇ y ⁇ 1, z satisfies 4 ⁇ z ⁇ 0, and w is 1 ⁇ w ⁇ 0 is satisfied, and at least one of z and w is 1 or more.
- the conventional positive electrode active material for a sodium battery has a low operating potential of about 3.5 V or less, and a sodium battery having a sufficient energy density has not been realized.
- the operating potential tends to decrease greatly.
- LiCoO 2 exhibits a potential of about 4 V
- the average of Na (x) CoO 2 The potential is about 2.9 V, which is significantly lower than that of LiCoO 2 .
- Na ions have a larger ionic radius than Li ions, it has been considered that Na ions are difficult to move when Li in the Li-containing active material is replaced with Na.
- it is a general knowledge that in a lithium battery active material simply replacing lithium with sodium does not yield a useful high-potential-operated sodium battery active material. It was.
- a compound represented by Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) can be used as a positive electrode active material of a sodium battery. It has been found that it operates in an ultrahigh potential region such as 4.9V.
- the potential range of 4.6 to 4.9 V is a potential range where the decomposition of the electrolytic solution used in combination with the positive electrode active material can be suppressed. Therefore, by using the positive electrode active material of the present invention, the potential range is stable over a long period of time. A sodium battery exhibiting battery characteristics can be obtained.
- the present inventor has obtained a compound represented by Na 4 Mn 3 (PO 4 ) 2 (P 2 O 7 ), a compound represented by Na 4 Co 3 (PO 4 ) 2 (P 2 O 7 ), Na 4 Co represented by (3-a) Mn a ( PO 4) compounds represented by 2 (P 2 O 7), Na 4 Co (3-b-c) Mn c Ni c (PO 4) 2 (P 2 O 7)
- Each of these compounds can also be used as a positive electrode active material for sodium batteries and has been found to operate in a high potential region exceeding 4V.
- the positive electrode active material of the present invention can exhibit high potential operability even in a relatively low temperature range of 25 ° C.
- the general formula (1) Na x M y ( AO 4) z (P 2 O 7) compounds represented by w, said Na 4 Ni 3 (PO 4) similar to 2 (P 2 O 7) or the like, sodium batteries As a positive electrode active material, it can operate in a high potential region.
- M is an electrochemically active divalent or higher-valent transition metal and has an ionic radius close to Ni or Ni.
- A is easy to take a tetrahedral structure like P or P similarly.
- the tetrahedral structure is a structure in which one A covalently bonded to these four oxygen atoms is contained in a tetrahedral void having four oxygen atoms as apexes.
- (AO 4 ) and (P 2 O 7 ) that are polyanion parts at least one of z representing the composition ratio of (AO 4 ) in the positive electrode active material and w representing the composition ratio of (P 2 O 7 ) Is 1 or more, it is considered that the positive electrode active material obtained operates in a high potential region due to the inductive effect on the MO bond by at least one of (AO 4 ) and (P 2 O 7 ).
- the inductive effect means that the A—O bond constituting (AO 4 ) and the P—O bond constituting (P 2 O 7 ) have high covalent bonds, so that the M—O bond electrons are converted into A—O bonds and P— As a result of being pulled to the -O bond side, the covalent bond between M and O is reduced, and the energy gap of the mixed orbitals is reduced. As a result, the redox level of M is lowered and the energy difference from sodium is increased. That is, the redox potential of sodium increases.
- the M may be at least one metal species selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. In this state, it is preferably divalent. This is because when M is a metal species that is divalent in a state before charging, it can operate at a high potential by being in a highly oxidized state of trivalent or higher during charging.
- Mn, Co, and Ni are particularly preferable. This is because Mn, Co, and Ni are divalent in a state before charging, and Mn and Co can form a crystal structure similar to Ni.
- Mn, Co, and Ni are divalent in a state before charging, and Mn and Co can form a crystal structure similar to Ni.
- Mn, Co, and Ni are partly selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn (ie, Mn, Co, and Ni). It may be substituted with at least one different from at least one selected from Ni).
- Ni when M is Ni, a positive electrode active material having high electron conductivity can be obtained.
- the redox element that is, the element that transmits and receives electrons is Ni
- the Ni ion oxide has a general olivine type crystal structure due to the desorption of Na ions during charging.
- the valence of Ni ions is larger than the valence of 2 to 3 (for example, Na 4 Ni 3 (PO 4 ) 2 In the case of (P 2 O 7 ), it is considered that the number of electrons changes to about 3.3 and more electrons move.
- Ni may be substituted with at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, and Zn.
- M Mn
- An active material can be obtained. Since the operating potential is relatively low, decomposition degradation of the electrolytic solution can be further suppressed.
- M Mn
- a part of Mn may be substituted with at least one selected from the group consisting of Ti, V, Cr, Fe, Co, Ni, Cu and Zn.
- M when M is Co, when a part of Co is substituted with Mn, more excellent capacity characteristics can be exhibited as compared with the case where M is only Co. This is considered to be because by replacing a part of the Co 2+ site with Mn 2+ , the substituted Mn 2+ can compensate for not only Mn 2 + / 3 + but also Mn 3 + / 4 + .
- a part of Co and Mn may be substituted with at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
- M is Co in the above formula (1)
- Mn and Ni when a part of Co is substituted with Mn and Ni, the M is compared with a case where Co is partially substituted with Mn. , May exhibit a higher working potential. This is because the substituted Mn 2+ can compensate for not only Mn 2 + / 3 + but also Mn 3 + / 4 + , and Ni in which charge compensation (Ni 2+ ⁇ Ni 3+ ) proceeds in a higher potential region compared to Co. This is considered to replace Co.
- a part of Co, Mn and Ni may be substituted with at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
- the A may be at least one selected from the group consisting of Al, Si, P, S, Ti, V and W, but selected from the group consisting of Si, P and S. It is preferable that it is at least one kind. This is because Si, P, and S are particularly easy to form a tetrahedral structure, and Si and S can form a crystal structure similar to P. Among these, A is preferably P. Incidentally, a part of these Si, P, and S is selected from the group consisting of Al, Si, P, S, Ti, V, and W. At least one selected from A (that is, Si, P, and S) It may be substituted with at least one species different from the species.
- x satisfies 4 ⁇ x ⁇ 2
- y satisfies 4 ⁇ y ⁇ 1
- z satisfies 4 ⁇ z ⁇
- w satisfies 1 ⁇ w ⁇ 0, and z and w
- particularly preferable positive electrode active materials include compounds represented by Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ).
- Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) contains Ni as a redox element and has (PO 4 ) and (P 2 O 7 ) as a polyanion part. In addition to such high electronic conductivity, it has high potential operability due to a high inductive effect.
- Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) has a crystal structure belonging to the space group Pn2 1 a.
- FIGS. 1 to 3 show the crystal structure (Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 )) belonging to the space group Pn2 1 a as seen from the a-axis direction (FIG. 1), from the b-axis direction.
- the figure (FIG. 2) seen and the figure (FIG. 3) seen from c-axis direction are shown.
- the crystal structure belonging to the space group Pn2 1 a is shown by taking Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) as an example, but in FIGS.
- M for example, Co or Mn
- the positive electrode active material of the present invention preferably has a crystal structure belonging to the space group Pn2 1 a.
- particularly preferable positive electrode active materials include compounds represented by the general formula Na 4 Mn 3 (PO 4 ) 2 (P 2 O 7 ), and a general formula Na 4 Co 3 (PO 4).
- ) 2 compound represented by P 2 O 7
- These compounds are all have a crystal structure belonging to space group Pn2 1 a shown in FIGS.
- Na 4 Mn 3 (PO 4 ) 2 (P 2 O 7 ) containing Mn as a redox element has improved reversibility and stability of the crystal structure and suppressed deterioration of the electrolyte. High cycle characteristics can be expressed.
- the general formula Na 4 Co 3 (PO 4 ) 2 (P 2 O 7 ) containing Co as a redox element is improved in reversibility and stability of the crystal structure, electrolyte solution By suppressing deterioration of the resin and increasing the reversible capacity, excellent cycle characteristics and capacity characteristics can be exhibited.
- Na 4 Co (3- a) Mn a (PO 4) 2 (P 2 O 7) is already as described above, by charge compensation with Mn, more excellent capacity characteristics can be exhibited as compared with Na 4 Co 3 (PO 4 ) 2 (P 2 O 7 ).
- O 7 ) is Na 4 Co (3-a) Mn a (PO 4 ) 2 (P 2 ) due to the charge compensation effect in the high potential region due to Ni in addition to the charge compensation effect due to Mn. Compared to O 7 ), a higher working potential can be developed.
- b representing the substitution amount of Mn
- the method for producing the positive electrode active material of the present invention is not particularly limited, but a preferable method includes the method for producing the positive electrode active material of the present invention described below.
- the method for producing a positive electrode active material for a sodium battery according to the present invention comprises: A method for producing a positive electrode active material for a sodium battery according to the present invention, A calcining step of calcining a raw material mixture containing at least an Na-containing compound, an M-containing compound containing M, an A-containing compound containing A, and a P-containing compound at 150 to 500 ° C. in an air atmosphere; After the preliminary firing, a final firing step of firing the obtained temporary fired product at 500 to 800 ° C. in an air atmosphere; It is characterized by including.
- the raw material mixture is first temporarily calcined at 150 to 500 ° C., lower than that in the main firing step, and then main calcined at 500 to 800 ° C., whereby the reaction proceeds uniformly and the single-phase positive electrode active material is activated. Substances can be synthesized.
- the pre-baking step is a step of baking a raw material mixture including at least a Na-containing compound, an M-containing compound, an A-containing compound, and a P-containing compound at 150 to 500 ° C. in an air atmosphere.
- Na-containing compound, M-containing compound, A-containing compounds, and P-containing compound the positive electrode active material Na x M y (AO 4) z (P 2 O 7) is a raw material of w, respectively, Na source, M source, A source and P source.
- the Na-containing compound, M-containing compound, A-containing compound and P-containing compound are not particularly limited, and can be appropriately selected. Each compound may be used individually by 1 type, or may be used in combination of 2 or more type. One compound may contain two or more of Na, M, A and P. When M and A contain a common atom, the M-containing compound and the A-containing compound may be the same compound, and when A is P, the A-containing compound and the P-containing compound are The same compound may be used.
- Na-containing compound that is the Na source examples include Na 2 CO 3 , Na 2 O, Na 2 O 2 , Na 3 PO 4 , Na 4 P 2 O 7, and CH 3 COONa.
- M-containing compound as the M source examples include Ti-containing compounds such as TiO 2 and Ti 2 O 3 , V-containing compounds such as V 2 O 3 , V 2 O 5 , and NH 4 VO 3 , Cr
- the containing compound examples include Cr 2 O 3 and Cr (NO 3 ) 3.
- Mn-containing compound examples include MnCO 3 and (CH 3 COO) 2 Mn.
- Fe-containing compound examples include FeO, Fe 2 O 3 , and Fe.
- Co-containing compounds such as CoCO 3 , (CH 3 COO) 2 Co, CoO, and Co 2 O 3 , and the like
- Ni-containing compounds such as (CH 3 COO) 2 Ni, NiCO 3 , and NiO etc.
- Cu-containing compounds include (CH 3 COO) 2 Cu, and CuO or the like, as Zn-containing compound, (CH 3 COO) 2 Zn , and, ZnO and the like
- Examples of the A-containing compound as the A source include Al (NO 3 ) 3 , Al 2 O 3 , and Al (OH) 3 as the Al-containing compound, SiO 2 and SiO, etc. as the Si-containing compound, P Examples of the compound containing NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , H 3 PO 4 , Na 2 P 2 O 7, and Na 3 PO 4, such as S-containing compounds (NH 4 ) 2 SO 4 , Na 2 SO 4 and H 2 SO 4, etc. Ti-containing compounds such as TiO 2 and Ti 2 O 3 , V-containing compounds such as V 2 O 3 , V 2 O 5 , NH 4 VO 3, etc. W containing Examples of the compound include WO 3 and Na 2 WO 4 .
- P-containing compounds that are P sources include NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , H 3 PO 4 , Na 4 P 2 O 7, and Na 3 PO 4 .
- Raw material mixture, the Na-containing compound, M-containing compound, the mixing ratio of the A-containing compounds and P-containing compounds, synthesized Na x M y (AO 4) z (P 2 O 7) x in w, y, z, And w may be set as appropriate.
- the preparation method of a raw material mixture is not specifically limited, Arbitrary mixing methods, stirring methods, etc. are employable.
- the size of the particles of each compound is not particularly limited, but in order to make the reaction proceed uniformly, it is preferable that the contact area between the particles is large. Therefore, each compound is pulverized before calcination. It is preferable. That is, it is preferable to provide a pulverization step for pulverizing the Na-containing compound, the M-containing compound, the A-containing compound, and the P-containing compound in the raw material mixture before temporary firing. In the pulverization step, compound pulverization may be performed simultaneously for a plurality of compounds or for each compound.
- the pulverization method in the pulverization step is not particularly limited, and any method can be adopted, and a method that combines mixing, stirring, and pulverization of the raw material mixture can also be employed.
- a ball mill, a bead mill, and the like can be mixed and stirred while pulverizing the raw material mixture.
- the calcination temperature is lower than that in the main calcination step and may be in the range of 150 to 500 ° C., but is preferably 180 to 450 ° C., more preferably 250 to 350 ° C.
- the calcination time is not particularly limited and may be set as appropriate. For example, it may be about 1 to 5 hours.
- the air atmosphere that is the atmosphere of the pre-baking step means an oxygen-containing gas atmosphere.
- the main baking step is a step of baking the pre-baked product obtained in the pre-baking step at 500 to 800 ° C. in an air atmosphere.
- the firing temperature in the main firing step is preferably 550 to 750 ° C.
- the main baking time is not particularly limited and may be set as appropriate. For example, it may be about 1 to 30 hours.
- the air atmosphere that is the atmosphere of the main baking step is the same as the air atmosphere of the temporary baking step.
- the manufacturing method of the positive electrode active material of this invention is not limited to the said method.
- it can be manufactured by the following method. That is, first, an Na-containing compound as a Na source, an M-containing compound as an M source, an A-containing compound as an A source, and a P-containing compound as a P source are dissolved in an acidic solution together with a gelling agent. Heat to prepare gel. Next, the obtained gel is baked in an air atmosphere.
- the Na-containing compound, the M-containing compound, the A-containing compound, and the P-containing compound may be appropriately selected as long as they can be dissolved in an acidic solution.
- Each compound may be used individually by 1 type, or may be used in combination of 2 or more type.
- One compound may contain two or more of Na, M, A and P.
- M and A contain a common atom
- the M-containing compound and the A-containing compound may be the same compound
- a is P the A-containing compound and the P-containing compound are The same compound may be used.
- examples of the Na-containing compound include Na 4 P 2 O 7 , CH 3 COONa, Na 2 CO 3 , Na 2 O, and Na 2 O 2 .
- M-containing compounds include Ti-containing compounds such as Ti (NO 3 ) 4 , TiO 2 , and Ti 2 O 3 , V-containing compounds such as V 2 O 3 and V 2 O 5 , and Cr-containing compounds. , Cr (NO 3 ) 3, etc., as Mn-containing compounds, (CH 3 COO) 2 Mn, and MnCO 3, etc., Fe-containing compounds such as Fe (NO 3 ) 3 , FeC 2 O 4 , and (CH 3 COO) 3 Fe and the like, Co-containing compounds such as (CH 3 COO) 2 Co, CoCO 3 , Co 2 O 3 , and CoO, and Ni-containing compounds such as (CH 3 COO) 2 Ni, NiO, and NiCO 3 , Cu
- the containing compound include (CH 3 COO) 2 Cu
- examples of the Zn-containing compound include (CH 3 COO) 2 Zn.
- Examples of the A-containing compound include Al (NO 3 ) 3 as the Al-containing compound, Si (OCH 2 CH 3 ) 4 as the Si-containing compound, NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , H 3 PO 4, etc., S-containing compounds such as H 2 SO 4 and Na 2 SO 4, etc.
- Ti containing compounds such as Ti (NO 3 ) 4 , TiO 2 , Ti 2 O 3 etc.
- V-containing compound include V 2 O 3 and V 2 O 5
- examples of the W-containing compound include WO 3 and Na 2 WO 4 .
- Examples of the P-containing compound include NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , and H 3 PO 4 .
- the mixing ratio of the Na-containing compound, the M-containing compound, the A-containing compound, and the P-containing compound depends on x, y, z, and w in Na x M y (AO 4 ) z (P 2 O 7 ) w to be synthesized. Can be set as appropriate.
- gelling agent examples include glycolic acid.
- an acidic solution examples include nitric acid aqueous solution etc. are mentioned, for example.
- the heating temperature at the time of gel preparation is not particularly limited as long as the above-mentioned compounds can be dissolved in an acidic solution to prepare a gel, and can be set to 60 to 120 ° C., for example.
- the firing temperature of the gel can be, for example, 500 to 800 ° C., and preferably 550 to 750 ° C.
- the air atmosphere at the time of gel baking is the same as the air atmosphere in the preliminary baking step.
- the positive electrode active material provided by the present invention can be suitably used as a positive electrode active material for sodium batteries.
- the sodium battery may be a primary battery or a secondary battery.
- a sodium battery using the positive electrode active material provided by the present invention will be described taking a sodium secondary battery as an example.
- FIG. 4 is a schematic cross-sectional view showing one embodiment of a sodium secondary battery.
- the sodium secondary battery 8 usually has a structure in which the electrolyte layer 3 is interposed between the negative electrode 1 and the positive electrode 2.
- the negative electrode 1 includes a negative electrode active material layer 4 containing a negative electrode active material, and a negative electrode current collector 5 that collects current from the negative electrode active material layer 4.
- the positive electrode 2 includes a positive electrode active material layer 6 containing a positive electrode active material and a positive electrode current collector 7 that collects current from the positive electrode active material layer 6.
- Each configuration will be described below.
- the negative electrode contains a negative electrode active material capable of releasing and capturing sodium ions.
- the negative electrode usually has a negative electrode active material layer containing at least a negative electrode active material, and further includes a negative electrode current collector that collects current from the negative electrode active material layer as necessary.
- the negative electrode active material examples include hard carbon, Na metal, tin, and the like.
- the negative electrode active material layer may contain only the negative electrode active material, but may contain a binder, a conductive material, an electrolyte and the like in addition to the negative electrode active material.
- a negative electrode layer containing only the negative electrode active material can be obtained.
- the negative electrode active material is in a powder form, a negative electrode layer containing a binder in addition to the negative electrode active material can be obtained.
- binder examples include polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), and the like.
- conductive material examples include carbon materials such as carbon black, activated carbon, carbon carbon fiber (eg, carbon nanotube, carbon nanofiber, etc.), graphite, and the like.
- the positive electrode contains a positive electrode active material capable of releasing and capturing sodium ions.
- the positive electrode usually has a positive electrode active material layer containing at least a positive electrode active material, and further includes a positive electrode current collector that collects the positive electrode active material layer as necessary.
- the positive electrode active material As the positive electrode active material, the positive electrode active material of the present invention or the positive electrode active material manufactured by the manufacturing method of the present invention can be used. Similar to the negative electrode active material layer, the positive electrode active material layer may contain only the positive electrode active material, but contains a conductive material, a binder, an electrolyte, an electrode catalyst, etc. in addition to the positive electrode active material. You may do. About the electroconductive material and binder in a positive electrode active material, since the material similar to a negative electrode active material layer can be used, description here is abbreviate
- the negative electrode active material layer and the positive electrode active material layer can be prepared by, for example, slurry containing each material by any coating method such as a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, and a screen printing method.
- the electrode active material layer can be formed by coating, drying, and rolling as necessary.
- the positive electrode current collector and the negative electrode current collector are not particularly limited in material, structure, and shape as long as the materials have desired electronic conductivity and do not cause an alloying reaction with sodium ions in the battery environment.
- the material for the positive electrode current collector include metal materials such as stainless steel, nickel, aluminum, iron, titanium, and copper, carbon materials such as carbon fiber and carbon paper, and high electron conductive ceramic materials such as titanium nitride. It is done.
- the battery case may have a function as a positive electrode current collector.
- Examples of the material for the negative electrode current collector include copper, stainless steel, nickel, and aluminum.
- the battery case may have a function as a negative electrode current collector.
- the shape of the positive electrode current collector and the negative electrode current collector include a plate shape, a foil shape, and a mesh shape, and a mesh shape is preferable.
- the electrolyte layer contains at least an electrolyte that enables conduction of sodium ions between the positive electrode and the negative electrode.
- the electrolyte only needs to have sodium ion conductivity, and examples thereof include an electrolyte, a gel electrolyte obtained by gelling the electrolyte using a polymer, a solid electrolyte, and the like.
- Examples of the electrolytic solution having sodium ion conductivity include an electrolytic solution in which a sodium salt is dissolved in an aqueous solvent or a non-aqueous solvent.
- the non-aqueous solvent is not particularly limited, and examples thereof include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), and fluoroethylene carbonate (FEC), cyclic esters such as ⁇ -butyrolactone (GBL), and dimethyl carbonate. Examples thereof include chain carbonates such as (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). These nonaqueous solvents may be used alone or in combination of two or more. Further, a nitrile compound in which a CN group is bonded to the end of the chain saturated hydrocarbon compound may be used by mixing with a non-aqueous solvent.
- cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), and fluoroethylene carbonate (FEC)
- cyclic esters such as ⁇ -butyrolactone (GBL)
- dimethyl carbonate examples thereof include chain carbonates such as (DMC), diethyl carbonate (
- a nitrile compound By adding a nitrile compound to a non-aqueous solvent electrolyte, a stable non-aqueous solvent electrolyte that does not decompose can be obtained even in a high potential region where the positive electrode active material for a sodium battery of the present invention operates. it can.
- the sodium salt is not particularly limited, for example, NaPF 6, NaBF 4, NaClO 4, NaCF 3 SO 3, (CF 3 SO 2) 2 NNa, NaN (FSO 2), NaC (CF 3 SO 2) 3 , etc. Is mentioned. These sodium salts may be used individually by 1 type, and may be used in combination of 2 or more type. NaPF 6 which is stable even in a high potential region is particularly preferable. In the non-aqueous electrolyte, the concentration of sodium salt is not particularly limited.
- the non-aqueous electrolyte can be used after adding a polymer to gel.
- the gelation method of the nonaqueous electrolyte include, for example, a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF), or polymethyl methacrylate (PMMA). The method of adding is mentioned.
- the electrolyte When an electrolytic solution is used as the electrolyte, it is possible to ensure insulation between the positive electrode and the negative electrode by disposing a separator that is an insulating porous body between the positive electrode and the negative electrode and impregnating the separator with the electrolytic solution.
- a separator examples include porous membranes such as polyethylene porous membrane and polypropylene porous membrane; and nonwoven fabrics such as resin nonwoven fabric and glass fiber nonwoven fabric.
- a battery case that accommodates the negative electrode, the electrolyte layer, and the positive electrode for example, a battery case having a general shape such as a coin shape, a flat plate shape, a cylindrical shape, or a laminate shape can be used.
- a separator made of an insulating material between the positive electrode and the negative electrode can be provided. Examples of such a separator include porous membranes such as polyethylene porous membrane and polypropylene porous membrane; and nonwoven fabrics such as resin nonwoven fabric and glass fiber nonwoven fabric.
- the current collector of each electrode can be provided with a terminal serving as a connection portion with the outside.
- the upper diagram is an XRD pattern of the synthesized product
- the lower diagram is an XRD pattern of Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 (ICSD No. 01-087-0977) in the ICSD database.
- the obtained composite was Na 4 Ni 3 (PO 4 ) 2 P 2 O 7
- the obtained composite Na 4 Ni 3 (PO 4 ) 2 P 2 O 7
- the obtained composite Na 4 Ni 3 (PO 4 ) 2 P 2 O 7
- the obtained composite Na 4 Ni 3 (PO 4 ) 2 P 2 O 7
- the obtained composite has a crystal structure belonging to the space group Pn2 1 a.
- Example 1 As shown in FIG. 6, in both the first and second cycles, an oxidation reaction corresponding to charging and a reduction reaction peak corresponding to discharging were confirmed in an ultrahigh potential region of 4.6 to 4.9 V. That is, it was confirmed that the composite obtained in Example 1 can be used as a positive electrode active material of a sodium secondary battery and operates at a high potential. Moreover, the above high potential operability was exhibited in a low temperature range of 25 ° C.
- the obtained composite was Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 . Further, it was confirmed that the obtained composite (Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 ) has a crystal structure belonging to the space group Pn2 1 a shown in FIGS.
- a coin-type evaluation cell was produced in the same manner as in Example 1 except that diethyl carbonate (DEC) was used instead of dimethyl carbonate (DMC).
- DEC diethyl carbonate
- DMC dimethyl carbonate
- Example 2 As shown in FIG. 8, after 10 cycles, it is possible to charge and discharge in the same potential region as the first cycle, and to maintain the discharge capacity density (capacity maintenance rate 96%, reversible capacity 18 mAh / g). Was confirmed. That is, it was found that the positive electrode active material of Example 2 can be charged and discharged in a potential region where the electrolyte solution is stable, and is excellent in cycle characteristics.
- FIG. 10 shows the relationship between the capacity density and the potential in the first cycle and the 50th cycle.
- FIG. 11 shows the relationship between the number of cycles, the charge capacity density, and the discharge capacity density.
- FIG. 12 shows a charge curve and a discharge curve at the 10th cycle. -Potential range: 3.0V-4.8V ⁇ Current density: 1700 mA / g ⁇ Temperature: 25 °C
- Example 3 As shown in FIG. 10, after 50 cycles, it was possible to charge and discharge in the same potential region as in the first cycle, and an increase in reversible capacity was confirmed as compared with Examples 1 and 2. Further, as shown in FIG. 11, it was confirmed that the capacity density could be maintained even after 50 cycles. That is, it was found that the positive electrode active material of Example 3 had a high reversible capacity (about 90 mAh / g) in a potential region where the electrolyte solution was stable, and was excellent in cycle characteristics. Further, as shown in FIG. 12, a reversible capacity of about 82 mAh / g was exhibited even at an extremely high current density of 1700 mAh / g.
- the positive electrode active material of Example 3 has a high battery capacity because the capacity decrease is small despite the current density being 100 times that of the charge / discharge cycle test at a current density of 17 mA / g. It is considered to be an advantageous material for input / output.
- the crystal structures of the composites of Examples 4 to 8 obtained by firing were analyzed using an X-ray diffractometer (XRD). The results are shown in Table 2.
- the composites obtained in Examples 4 to 8 were Na 4 Co 3 (PO 4 ) 2 P 2 O 7 (Example 4) and Na 4 Co 2.7 Mn 0.3 (PO 4 ) 2 P, respectively.
- 2 O 7 (Example 5) Na 4 Co 2.4 Mn 0.6 (PO 4 ) 2 P 2 O 7 (Example 6), Na 4 Co 2.2 Mn 0.8 (PO 4 ) 2 P It was confirmed that they were 2 O 7 (Example 7) and Na 4 Co 2.1 Mn 0.9 (PO 4 ) 2 P 2 O 7 (Example 8). It was also confirmed that the composites obtained in Examples 4 to 8 had a crystal structure belonging to the space group Pn2 1 a shown in FIGS.
- Positive electrode active materials Na 4 Co 3.0 (PO 4 ) 2 P 2 O 7 (Example 4), Na 4 Co 2.7 Mn 0.3 (PO 4 ) 2 obtained in Examples 4 to 8 above.
- P 2 O 7 (Example 5), Na 4 Co 2.4 Mn 0.6 (PO 4 ) 2 P 2 O 7 (Example 6), Na 4 Co 2.2 Mn 0.8 (PO 4 ) 2 P 2 O 7 (Example 7), Na 4 Co 2.1 Mn 0.9 (PO 4 ) 2 P 2 O 7 (Example 8)) were respectively combined with a positive electrode active material, a conductive additive, and a binder.
- a slurry was prepared by dispersing in N-methyl-2-pyrrolidone (dispersant). Each of the above slurries was applied onto an aluminum foil (current collector), dried and rolled to produce a positive electrode in which the current collector and the positive electrode active material layer were laminated.
- FIG. 13 shows the relationship between the capacity density at the third cycle and the potential (discharge curve and charge curve).
- (a) is the result of Example 4
- (b) is the result of Example 5
- (c) is the result of Example 6,
- FIG. 14 shows the discharge curves of the third cycle of Examples 4 to 8.
- (a) to (e) correspond to (a) to (e) in FIG.
- FIG. 15 shows the cycle characteristics (relationship between the number of cycles and the discharge capacity density) of Examples 4 to 8.
- the crystal structures of the composites of Examples 9 to 12 obtained by firing were analyzed by an X-ray diffractometer (XRD). The results are shown in Table 4.
- the composites obtained in Examples 9 to 12 were respectively Na 4 Co 3 (PO 4 ) 2 P 2 O 7 (Example 9), Na 4 Co 2.4 Mn 0.3 Ni 0.3 (PO 4) 2 P 2 O 7 (example 10), Na 4 Co 1.0 Mn 1.0 Ni 1.0 (PO 4) 2 P 2 O 7 ( example 11), Na 4 Co 0.6 Mn 1 .2 Mn 1.2 (PO 4 ) 2 P 2 O 7 (Example 12) was confirmed. It was also confirmed that the composites obtained in Examples 9 to 12 had a crystal structure belonging to the space group Pn2 1 a shown in FIGS.
- Positive electrode active materials Na 4 Co 3.0 (PO 4 ) 2 P 2 O 7 (Example 9), Na 4 Co 2.4 Mn 0.3 Ni 0.3 ( PO 4 ) 2 P 2 O 7 (Example 10), Na 4 Co 1.0 Mn 1.0 Ni 1.0 (PO 4 ) 2 P 2 O 7 (Example 11), Na 4 Co 0.6 Mn 1.2 Mn 1.2 (PO 4 ) 2 P 2 O 7 (Example 12)
- FIG. 16 shows the relationship between the capacity density and potential at the third cycle (discharge curve and charge curve).
- (a) is the result of Example 9
- (b) is the result of Example 10
- (c) is the result of Example 11
- (d) is the result of Example 12.
- all of Examples 9 to 11 showed a very excellent discharge capacity of 90 to 95 mAh / g in a high potential region of 3.0 to 4.8 V.
- Example 12 exhibited a discharge capacity of 35 mAh / g in a high potential region of 3.0 to 4.8V.
- the Co 2+ site of Na 4 Co 3.0 (PO 4 ) 2 P 2 O 7 is represented by the general formula Na 4 Co (3-bc) Mn b Ni c (PO 4 ) 2 (P 2 O 7 Example 10 and 11 in which 0.3 ⁇ b ⁇ 1.0 and 0.3 ⁇ c ⁇ 1.0 were substituted with Mn 2+ and Ni 2+ in Example 9 (Na 4 Co 3) 0.0 (PO 4 ) 2 P 2 O 7 ), both capacitance characteristics and voltage characteristics were improved.
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Abstract
Description
リチウム電池は、上記したようにエネルギー密度や出力に優れる一方、リチウム電池の需要拡大に伴いリチウムの価格が上昇していることや、リチウムの埋蔵量が限られていること等が、量産や大型化のボトルネックとなっている。
例えば、特許文献1には、MaxMbyP2O7(MaはNa、Li、Ca、又はMgを表わし、Mbは4価以上で安定に存在する遷移金属を表わし、0≦x≦4、0.5≦y≦3、6≦z≦14である)で表わされる非水電解質二次電池用正極活物質が開示されている。特許文献1において、実施例で実際に作製、評価されているのは、MoP2O7である。
一般式(1)
NaxMy(AO4)z(P2O7)w
(式(1)中、Mは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる少なくとも1種であり、Aは、Al、Si、P、S、Ti、V及びWよりなる群から選ばれる少なくとも1種であり、xは4≧x≧2を満たし、yは4≧y≧1を満たし、zは4≧z≧0を満たし、wは1≧w≧0を満たし、z及びwの少なくとも一方は1以上である。)
本発明のナトリウム電池用正極活物質のより好ましい具体的な形態として、前記式(1)中、前記Mが、Niであり、Niの一部が、Ti、V、Cr、Mn、Fe、Co、Cu及びZnよりなる群から選ばれる少なくとも1種で置換されていてもよいものが挙げられる。
本発明のナトリウム電池用正極活物質のより好ましい具体的な形態として、前記式(1)中、前記Aは、Pであり、Pの一部が、Al、Si、S、Ti、V及びWよりなる群から選ばれる少なくとも1種で置換されていてもよいものが挙げられる。
少なくとも、Na含有化合物、前記Mを含むM含有化合物、前記Aを含むA含有化合物、及び、P含有化合物を含む原料混合物を、大気雰囲気下、150~500℃で焼成する仮焼成工程と、
前記仮焼成後、得られた仮焼成物を、大気雰囲気下、500~800℃で焼成する本焼成工程と、
を含むことを特徴とするものである。
本発明のナトリウム電池用正極活物質の製造方法は、前記仮焼成工程の前に、前記Na含有化合物、前記M含有化合物、前記A含有化合物、及び、前記P含有化合物を粉砕する粉砕工程を含んでいてもよい。
本発明のナトリウム電池用正極活物質は、下記一般式(1)で表わされることを特徴とするものである。
一般式(1)
NaxMy(AO4)z(P2O7)w
(式(1)中、Mは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる少なくとも1種であり、Aは、Al、Si、P、S、Ti、V及びWよりなる群から選ばれる少なくとも1種であり、xは4≧x≧2を満たし、yは4≧y≧1を満たし、zは4≧z≧0を満たし、wは1≧w≧0を満たし、z及びwの少なくとも一方は1以上である。)
また、リチウム電池用活物質のLiをNaに置き換えた場合、その作動電位は大きく低下するという傾向がある。例えば、上記非特許文献5に記載されているように、LiCoO2が4V程度の電位を示すのに対して、上記非特許文献4に記載されているように、Na(x)CoO2の平均電位は2.9V程度であり、LiCoO2に比べて大きく低下する。
また、従来、NaイオンがLiイオンと比較してイオン半径が大きいために、Li含有活物質のLiをNaに置換した場合、Naイオンが動きにくくなると考えられてきた。
以上のような理由から、リチウム電池用の活物質において、単にリチウムをナトリウムに置換しても、有用な高電位作動型のナトリウム電池用活物質は得られないというのが一般的な知見であった。
その上、本発明の正極活物質は、25℃という比較的低温域においても、高電位作動性を発現することができる。
すなわち、一般式(1)において、Mは、電気化学的に活性な2価以上の遷移金属であり、Ni又はNiに近いイオン半径を有するものである。
また、一般式(1)において、Aは、P、又は、Pと同様、四面体構造をとりやすいものである。ここで四面体構造とは、4つの酸素原子を頂点とする四面体の空隙に、これら4つの酸素原子と共有結合した1つのAが入った構造である。
また、ポリアニオン部である(AO4)及び(P2O7)については、正極活物質における(AO4)の組成比を表わすz及び(P2O7)の組成比を表わすwの少なくとも一方が1以上であれば、(AO4)及び(P2O7)の少なくとも一方による、M-O結合に対するinductive効果により、得られる正極活物質は高電位域で作動すると考えられる。inductive効果とは、(AO4)を構成するA-O結合及び(P2O7)を構成するP-O結合の高い共有結合性により、M-O結合の電子がA-O結合及びP-O結合側に引っ張られ、M-O間の共有結合性が低下し、混性軌道のエネルギーギャップが小さくなる結果、Mの酸化還元準位が下がり、ナトリウムとのエネルギー差が大きくなって対ナトリウムの酸化還元電位が高くなる、というものである。
本発明の正極活物質において、前記Mは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる少なくとも1種の金属種であればよく、中でも、充電前の状態において、2価であることが好ましい。Mが、充電前の状態において2価である金属種の場合、充電時に3価以上の高酸化状態となることで、高電位で作動可能であるからである。
尚、これらMn、Co、及びNiは、その一部が、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる、該M(すなわち、Mn、Co、及びNiから選ばれる少なくとも1種)と異なる少なくとも1種で置換されていてもよい。
尚、Coは、その一部が、Ti、V、Cr、Mn、Fe、Ni、Cu及びZnよりなる群から選ばれる、少なくとも1種で置換されていてもよい。
z及びwが共に1以上の場合、ポリアニオン部が、AO4四面体と、AO4四面体と1つの酸素を共有したP2O7と、を含むため、M-O結合に対するinductive効果が高くなり、その結果、より高電位な正極活物質が得られるため好ましい。
さらに、Na4Ni3(PO4)2(P2O7)は、空間群Pn21aに帰属する結晶構造を有している。図1~3に空間群Pn21aに帰属する結晶構造(Na4Ni3(PO4)2(P2O7))を、a軸方向から見た図(図1)、b軸方向から見た図(図2)、及びc軸方向から見た図(図3)を示す。尚、図1~3では、Na4Ni3(PO4)2(P2O7)を例に、空間群Pn21aに帰属する結晶構造を示したが、図1~3において、Niを上記Mのその他の金属種(例えば、CoやMn)に置き換えることによって、空間群Pn21aに帰属する結晶構造を有するその他の正極活物質の結晶構造が示される。
図1~3からわかるように、空間群Pn21aに帰属する結晶構造において、結晶構造中の全てのNaイオンが、a軸、b軸及びc軸のいずれかの方向に配列しており、Naイオンの移動性が非常に高い。すなわち、空間群Pn21aに帰属する結晶構造は、Naイオンの伝導に非常に有利であり、Naイオンの挿入・脱離がスムーズに進行する。
以上のような理由から、本発明の正極活物質は、空間群Pn21aに帰属する結晶構造を有することが好ましい。
一般式Na4Co(3-a)Mna(PO4)2(P2O7)において、Mnの置換量を表わすaは、3未満の数であればよいが、0.01≦a≦0.8の範囲内であることが好ましく、特に0.3≦a≦0.8の範囲であることが好ましく、中でもa=0.6であることが好ましい。
一般式Na4Co(3-b-c)MnbNic(PO4)2(P2O7)において、Mnの置換量を表わすb及びNiの置換量を表わすcは、その和(b+c)が3未満の数であればよいが、0.01≦b≦1.0且つ0.01≦c≦1.0の範囲内であることが好ましく、特に0.3≦b≦1.0且つ0.3≦c≦1.0の範囲であることが好ましい。
本発明の正極活物質を製造する方法は特に限定されないが、好ましい方法として、以下に説明する本発明の正極活物質の製造方法が挙げられる。
上記本発明のナトリウム電池用正極活物質の製造方法であって、
少なくとも、Na含有化合物、前記Mを含むM含有化合物、前記Aを含むA含有化合物、及び、P含有化合物を含む原料混合物を、大気雰囲気下、150~500℃で焼成する仮焼成工程と、
前記仮焼成後、得られた仮焼成物を、大気雰囲気下、500~800℃で焼成する本焼成工程と、
を含むことを特徴とするものである。
(仮焼成工程)
仮焼成工程は、Na含有化合物、M含有化合物、A含有化合物、及び、P含有化合物を少なくとも含む原料混合物を、大気雰囲気下、150~500℃で焼成する工程である。
原料混合物中、各化合物の粒子のサイズは特に限定されないが、反応を均一に進行させるためには、粒子間の接触面積が大きい方が好ましいことから、各化合物を仮焼成前に粉砕しておくことが好ましい。すなわち、仮焼成前に、原料混合物中のNa含有化合物、M含有化合物、A含有化合物及びP含有化合物を粉砕する粉砕工程を設けることが好ましい。粉砕工程において、化合物の粉砕は、複数の化合物を同時に行ってもよいし、各化合物ごとに行ってもよい。また、粉砕工程における粉砕方法は特に限定されず、任意の方法を採用することができ、原料混合物の混合や攪拌と粉砕とを兼ねる方法を採用することもできる。例えば、ボールミル、ビーズミル等は、原料混合物を粉砕しながら、混合、攪拌することもできる。
仮焼成工程の雰囲気である大気雰囲気とは、酸素含有ガス雰囲気を意味する。
本焼成工程は、仮焼成工程で得られた仮焼成物を、大気雰囲気下、500~800℃で焼成する工程である。
本焼成工程における焼成温度は、好ましくは550~750℃である。本焼成時間は、特に限定されず、適宜設定すればよいが、例えば、1~30時間程度とすることができる。
本焼成工程の雰囲気である大気雰囲気とは、仮焼成工程の大気雰囲気と同様である。
尚、本発明の正極活物質の製造方法は、上記方法に限定されない。例えば、以下の方法によって製造することも可能である。すなわち、まず、Na源であるNa含有化合物、M源であるM含有化合物、A源であるA含有化合物、及び、P源であるP含有化合物を、ゲル化剤と共に、酸性溶液中に溶解、加熱し、ゲルを調製する。次に、得られたゲルを、大気雰囲気下、焼成する方法である。
ゲルの焼成温度は、例えば、500~800℃とすることができ、好ましくは550~750℃である。ゲル焼成時の大気雰囲気とは、上記仮焼成工程の大気雰囲気と同様である。
本発明により提供される正極活物質は、ナトリウム電池の正極活物質として好適に使用することができる。ナトリウム電池は一次電池でも二次電池でもよい。以下、ナトリウム二次電池を例に、本発明により提供される正極活物質を用いたナトリウム電池について説明する。
以下、各構成について説明する。
負極活物質層は、負極活物質のみを含有するものであってもよいが、負極活物質の他に結着剤、導電性材料、電解質等を含有するものであってもよい。例えば、負極活物質が板状、箔状等である場合は、負極活物質のみを含有する負極層とすることができる。一方、負極活物質が粉末状である場合は、負極活物質に加えて結着剤を含有する負極層とすることができる。
結着剤としては、例えば、ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン(PTFE)、スチレンブタジエンゴム(SBR)等が挙げられる。導電性材料としては、例えば、カーボンブラック、活性炭、カーボン炭素繊維(例えばカーボンナノチューブ、カーボンナノファイバー等)、グラファイト等の炭素材料等を挙げることができる。
負極活物質層と同様、正極活物質層は、正極活物質のみを含有するものであってもよいが、正極活物質の他に導電性材料や、結着剤、電解質、電極触媒等を含有するものであってもよい。正極活物質における導電性材料、結着剤については、負極活物質層と同様の材料を用いることができるため、ここでの説明は省略する。
正極集電体の材料としては、例えば、ステンレス、ニッケル、アルミニウム、鉄、チタン、銅等の金属材料、カーボンファイバー、カーボンペーパー等のカーボン材料、窒化チタン等の高電子伝導性セラミックス材料等が挙げられる。電池ケースが正極集電体としての機能を兼ね備えていてもよい。
負極集電体の材料としては、銅、ステンレス、ニッケル、アルミニウム等が挙げられる。電池ケースが負極集電体としての機能を有していてもよい。
正極集電体及び負極集電体の形状としては、例えば、板状、箔状、メッシュ状等が挙げられ、中でもメッシュ状が好ましい。
電解質としては、ナトリウムイオン伝導性を有していればよく、例えば、電解液、電解液をポリマー等を用いてゲル化したゲル状電解質、固体電解質等が挙げられる。
ナトリウムイオン伝導性を有する電解液としては、例えば、ナトリウム塩を、水系溶媒又は非水溶媒に溶解した電解液が挙げられる。
非水電解液において、ナトリウム塩の濃度は特に限定されない。
正極、電解質層、負極の順番で配置されている積層体を、繰り返し何層も重ねる構造を取る電池の場合には、安全性の観点から、正極および負極の間に、絶縁性材料からなるセパレータを備えることができる。このようなセパレータとしては、例えばポリエチレン多孔膜、ポリプロピレン多孔膜等の多孔膜;および樹脂不織布、ガラス繊維不織布等の不織布等を挙げることができる。
また、各電極の集電体には、それぞれ、外部との接続部となる端子を設けることができる。
(ナトリウム電池用正極活物質の合成)
Na2CO3(Na含有化合物)、(CH3COO)2Ni(Ni含有化合物)、及びNH4H2PO4(P含有化合物)を、Na:Ni:P=4:3:4(mol比)となるように混合した。混合物をボールミルを用いて粉砕した後、大気雰囲気下、300℃で仮焼成を行い、さらに、700℃、15時間で本焼成を行った。
本焼成によって得られた合成物の結晶構造を、X線回折装置(XRD)により分析した。結果を図5に示す。図5において、上図は、合成物のXRDパターンであり、下図は、ICSDデータベースのNa4Ni3(PO4)2P2O7(ICSD No.01-087-0977)のXRDパターンである。図5より、得られた合成物は、Na4Ni3(PO4)2P2O7であることが確認できた。また、得られた合成物(Na4Ni3(PO4)2P2O7)が、空間群Pn21aに帰属する結晶構造を有することが確認された。
<正極の作製>
上記実施例1で得られたNa4Ni3(PO4)2P2O7(正極活物質)、炭素(導電助剤)、及びPVdF(結着剤)を、75:20:5(重量比)となるように混合し、N-メチル-2-ピロリドン(分散剤)中に分散させてスラリーを調製した。
上記スラリーをアルミニウム箔(集電体)上に塗布し、乾燥及び圧延し、集電体と正極活物質層とが積層した正極を作製した。
まず、箔状のナトリウム金属を打ち抜き、対極を得た。
一方、エチレンカーボネート(EC)とジメチルカーボネート(DMC)とを1:1(体積比)で混合した混合溶媒に、ナトリウム塩(NaPF6)を添加し、ナトリウム塩濃度が1.0mol/dm3の非水溶媒系電解液を得た。
上記にて作製した正極、ポリプロピレン製多孔質膜とポリエチレン製多孔質膜とポリプロピレン製多孔質膜とがこの順序で積層した多孔質膜(セパレータ)、及び対極を、この順序で積層した。このとき、正極活物質層がセパレータ側となるように正極を積層した。
上記積層体のセパレータに上記非水溶媒系電解液を含浸させ、コイン型の評価用セルを作製した。
上記評価用セルを用いて、サイクリックボルタンメトリ-(CV)を下記条件にて行った。結果を図6に示す。
・電位範囲:OCV(開回路電圧)-4.9V
・走査速度:0.2mV/s
・温度:25℃
(ナトリウム電池用正極活物質の合成)
Na4P2O7(Na含有化合物兼P含有化合物)、(CH3COO)2Mn(Mn含有化合物)、及びNH4H2PO4(P含有化合物)を、Na:Mn:P=4:3:4(mol比)となるように、グリコール酸(ゲル化剤)と共に、酸性溶液(硝酸水溶液)中に添加、溶解し、80℃で攪拌した。得られたゲルを、大気雰囲気下、700℃で15時間、焼成した。
焼成によって得られた合成物の結晶構造を、X線回折装置(XRD)により分析した。結果を図7に示す。図7より、得られた合成物は、Na4Mn3(PO4)2P2O7であることが確認できた。また、得られた合成物(Na4Mn3(PO4)2P2O7)が、図1~3に示した空間群Pn21aに帰属する結晶構造を有することが確認された。
<正極の作製>
上記実施例2で得られたNa4Mn3(PO4)2P2O7(正極活物質)、炭素(導電助剤)、及びPVdF(結着剤)を、75:20:5(重量比)となるように混合し、N-メチル-2-ピロリドン(分散剤)中に分散させてスラリーを調製した。
上記スラリーをアルミニウム箔(集電体)上に塗布し、乾燥及び圧延し、集電体と正極活物質層とが積層した正極を作製した。
ジメチルカーボネート(DMC)の代わりにジエチルカーボネート(DEC)を用いたこと以外は、実施例1と同様にして、コイン型の評価用セルを作製した。
上記評価用セルの充放電サイクルを下記条件にて10サイクル行い、充放電特性を評価した。1サイクル目及び10サイクル目の容量密度と電位との関係を図8に示す。
・電位範囲:2.5V-4.1V
・電流密度:8.5mA/g
・温度:25℃
(ナトリウム電池用正極活物質の合成)
Na4P2O7(Na含有化合物兼P含有化合物)、(CH3COO)2Co(Co含有化合物)、及びNH4H2PO4(P含有化合物)を、Na:Co:P=4:3:4(mol比)となるように、グリコール酸(ゲル化剤)と共に、酸性溶液(硝酸水溶液)中に添加、溶解し、80℃で攪拌した。得られたゲルを、大気雰囲気下、700℃で15時間、焼成した。
焼成によって得られた合成物の結晶構造を、X線回折装置(XRD)により分析した。結果を図9に示す。図9より、得られた合成物は、Na4Co3(PO4)2P2O7であることが確認できた。また、得られた合成物(Na4Co3(PO4)2P2O7)が、図1~3に示した空間群Pn21aに帰属する結晶構造を有することが確認された。
<正極の作製>
上記実施例3で得られたNa4Co3(PO4)2P2O7(正極活物質)、炭素(導電助剤)、及びPVdF(結着剤)を、75:20:5(重量比)となるように混合し、N-メチル-2-ピロリドン(分散剤)中に分散させてスラリーを調製した。
上記スラリーをアルミニウム箔(集電体)上に塗布し、乾燥及び圧延し、集電体と正極活物質層とが積層した正極を作製した。
実施例2と同様にして、コイン型の評価用セルを作製した。
上記評価用セルの充放電サイクルを下記条件にて50サイクル行い、充放電特性を評価した。1サイクル目及び50サイクル目の容量密度と電位との関係を図10に示す。また、サイクル数と、充電容量密度及び放電容量密度との関係を図11に示す。
・電位範囲:3.0V-4.7V
・電流密度:17mA/g
・温度:25℃
また、上記評価用セルの充放電サイクルを下記条件にて行い、充放電特性を評価した。10サイクル目の充電曲線及び放電曲線を図12に示す。
・電位範囲:3.0V-4.8V
・電流密度:1700mA/g
・温度:25℃
(ナトリウム電池用正極活物質の合成)
Na4P2O7(Na含有化合物兼P含有化合物)、(CH3COO)2Co(Co含有化合物)、(CH3COO)2Mn(Mn含有化合物)、及びNH4H2PO4(P含有化合物)を、Na、Co、Mn及びPの比率が表1に示すモル比となるように、表1の仕込み量で、グリコール酸(ゲル化剤)と共に酸性溶液(硝酸水溶液)中に添加、溶解し、80℃で攪拌した。得られたゲルを、大気雰囲気下、700℃で15時間、焼成した。
実施例4~8で得られた合成物は、それぞれ、Na4Co3(PO4)2P2O7(実施例4)、Na4Co2.7Mn0.3(PO4)2P2O7(実施例5)、Na4Co2.4Mn0.6(PO4)2P2O7(実施例6)、Na4Co2.2Mn0.8(PO4)2P2O7(実施例7)、Na4Co2.1Mn0.9(PO4)2P2O7(実施例8)であることが確認できた。また、実施例4~8で得られた合成物が、図1~3に示した空間群Pn21aに帰属する結晶構造を有することが確認された。
<正極の作製>
上記実施例4~8で得られた正極活物質(Na4Co3.0(PO4)2P2O7(実施例4)、Na4Co2.7Mn0.3(PO4)2P2O7(実施例5)、Na4Co2.4Mn0.6(PO4)2P2O7(実施例6)、Na4Co2.2Mn0.8(PO4)2P2O7(実施例7)、Na4Co2.1Mn0.9(PO4)2P2O7(実施例8))を、それぞれ、正極活物質と、導電助剤と、結着剤との重量比が、75(正極活物質):20(導電助剤):5(結着剤)となるように、炭素(導電助剤)及びPVdF(結着剤)と混合し、N-メチル-2-ピロリドン(分散剤)中に分散させてスラリーを調製した。
上記スラリーを、それぞれ、アルミニウム箔(集電体)上に塗布し、乾燥及び圧延し、集電体と正極活物質層とが積層した正極を作製した。
実施例4~8の正極活物質を含む上記正極を用いて、実施例2と同様にして、コイン型の評価用セルを作製した。
上記評価用セルの充放電サイクルを下記条件にて3サイクル行い、充放電特性を評価した。
・電位範囲:実施例4;3.0V-4.7V、実施例5-8;3.0V-4.8V
・電流密度:17mA/g
・温度:25℃
また、図14に、実施例4~8の3サイクル目の放電曲線を示す。尚、図14中、(a)~(e)は、図13中の(a)~(e)に対応している。
また、図15に、実施例4~8のサイクル特性(サイクル数と放電容量密度の関係)を示す。
特に、Na4Co3.0(PO4)2P2O7のCo2+のサイトを、一般式Na4Co(3-a)Mna(PO4)2(P2O7)において0.3≦a≦0.8の割合で、Mn2+に置換した実施例5~7は、実施例4(Na4Co3.0(PO4)2P2O7)と比較して、容量特性及び電圧特性共に向上した。これは、Co2+のMn2+による置換の割合が上記範囲(0.3≦a≦0.8)である場合、置換されたMn2+が、Mn2+/3+だけでなく、4.7V以上の電位領域でMn3+/4+まで電荷補償することができることによる寄与が大きいためと考えられる。
尚、一般式Na4Co(3-a)Mna(PO4)2(P2O7)においてa=0.9の割合で、Co2+をMn2+に置換した実施例8は、Mn2+により、正極活物質の電子伝導性が低下したために、電池抵抗が増大し、実施例4(Na4Co3.0(PO4)2P2O7)と比較して、容量特性及び電圧特性が共に低下したと考えられる。
(ナトリウム電池用正極活物質の合成)
Na4P2O7(Na含有化合物兼P含有化合物)、(CH3COO)2Co(Co含有化合物)、(CH3COO)2Mn(Mn含有化合物)、(CH3COO)2Ni(Ni含有化合物)、及びNH4H2PO4(P含有化合物)を、Na、Co、Mn、Ni及びPの比率が表3に示すモル比となるように、表3の仕込み量で、グリコール酸(ゲル化剤)と共に酸性溶液(硝酸水溶液)中に添加、溶解し、80℃で攪拌した。得られたゲルを、大気雰囲気下、700℃で15時間、焼成した。
実施例9~12で得られた合成物は、それぞれ、Na4Co3(PO4)2P2O7(実施例9)、Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7(実施例10)、Na4Co1.0Mn1.0Ni1.0(PO4)2P2O7(実施例11)、Na4Co0.6Mn1.2Mn1.2(PO4)2P2O7(実施例12)であることが確認できた。また、実施例9~12で得られた合成物が、図1~3に示した空間群Pn21aに帰属する結晶構造を有することが確認された。
<正極の作製>
上記実施例9~12で得られた正極活物質(Na4Co3.0(PO4)2P2O7(実施例9)、Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7(実施例10)、Na4Co1.0Mn1.0Ni1.0(PO4)2P2O7(実施例11)、Na4Co0.6Mn1.2Mn1.2(PO4)2P2O7(実施例12))を、それぞれ、正極活物質と、導電助剤と、結着剤との重量比が、75(正極活物質):20(導電助剤):5(結着剤)となるように、炭素(導電助剤)及びPVdF(結着剤)と混合し、N-メチル-2-ピロリドン(分散剤)中に分散させてスラリーを調製した。
上記スラリーを、それぞれ、アルミニウム箔(集電体)上に塗布し、乾燥及び圧延し、集電体と正極活物質層とが積層した正極を作製した。
実施例9~12の正極活物質を含む上記正極を用いて、実施例2と同様にして、コイン型の評価用セルを作製した。
上記評価用セルの充放電サイクルを下記条件にて3サイクル行い、充放電特性を評価した。
・電位範囲:実施例9;3.0V-4.7V、実施例10-12;3.0V-4.8V
・電流密度:17mA/g
・温度:25℃
図16に示すように、実施例9~11のいずれも、3.0~4.8Vという高電位領域において、90~95mAh/gという非常に優れた放電容量を示した。実施例12については、3.0~4.8Vという高電位領域において、35mAh/gという放電容量を示した。
2…正極
3…電解質層
4…負極活物質層
5…負極集電体
6…正極活物質層
7…正極集電体
8…ナトリウム二次電池
Claims (14)
- 下記一般式(1)で表わされることを特徴とする、ナトリウム電池用の正極活物質。
一般式(1)
NaxMy(AO4)z(P2O7)w
(式(1)中、Mは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる少なくとも1種であり、Aは、Al、Si、P、S、Ti、V及びWよりなる群から選ばれる少なくとも1種であり、xは4≧x≧2を満たし、yは4≧y≧1を満たし、zは4≧z≧0を満たし、wは1≧w≧0を満たし、z及びwの少なくとも一方は1以上である。) - 前記式(1)中、前記Mが充電前において2価である、請求の範囲第1項に記載のナトリウム電池用正極活物質。
- 空間群Pn21aに帰属する結晶構造を有する、請求の範囲第1項又は第2項のいずれかに記載のナトリウム電池用正極活物質。
- 前記式(1)中、前記Mは、Mn、Co、及びNiより成る群から選ばれる少なくとも1種であり、その一部が、Ti、V、Cr、Mn、Fe、Co、Ni、Cu及びZnよりなる群から選ばれる、該Mと異なる少なくとも1種で置換されていてもよい、請求の範囲第1項乃至第3項のいずれかに記載のナトリウム電池用正極活物質。
- 前記式(1)中、前記Mは、Niであり、Niの一部が、Ti、V、Cr、Mn、Fe、Co、Cu及びZnよりなる群から選ばれる少なくとも1種で置換されていてもよい、請求の範囲第1項乃至第4項のいずれかに記載のナトリウム電池用正極活物質。
- 前記式(1)中、前記Aは、Si、P及びSより成る群から選ばれる少なくとも1種であり、その一部が、Al、Si、P、S、Ti、V及びWより成る群から選ばれる、該Aと異なる少なくとも1種で置換されていてもよい、請求の範囲第1項乃至第5項のいずれかに記載のナトリウム電池用正極活物質。
- 前記式(1)中、前記Aは、Pであり、Pの一部が、Al、Si、S、Ti、V及びWよりなる群から選ばれる少なくとも1種で置換されていてもよい、請求の範囲第1項乃至第6項のいずれかに記載のナトリウム電池用正極活物質。
- 一般式Na4Ni3(PO4)2(P2O7)で表わされる、請求の範囲第1項乃至第7項のいずれかに記載のナトリウム電池用正極活物質。
- 一般式Na4Mn3(PO4)2(P2O7)で表わされる、請求の範囲第1項乃至第7項のいずれかに記載のナトリウム電池用正極活物質。
- 一般式Na4Co3(PO4)2(P2O7)で表わされる、請求の範囲第1項乃至第7項のいずれかに記載のナトリウム電池用正極活物質。
- 一般式Na4Co(3-a)Mna(PO4)2(P2O7)(aは、0.3≦a≦0.8を満たす)で表わされる、請求の範囲第1項乃至第7項のいずれかに記載のナトリウム電池用正極活物質。
- 一般式Na4Co(3-b-c)MnbNic(PO4)2(P2O7)(bは、0.3≦b≦1.0を満たし、cは0.3≦c≦1.0を満たす)で表わされる、請求の範囲第1項乃至第7項のいずれかに記載のナトリウム電池用正極活物質。
- 請求の範囲第1項乃至第12項のいずれかに記載のナトリウム電池用正極活物質の製造方法であって、
少なくとも、Na含有化合物、前記Mを含むM含有化合物、前記Aを含むA含有化合物、及び、P含有化合物を含む原料混合物を、大気雰囲気下、150~500℃で焼成する仮焼成工程と、
前記仮焼成後、得られた仮焼成物を、大気雰囲気下、500~800℃で焼成する本焼成工程と、
を含むことを特徴とする、ナトリウム電池用正極活物質の製造方法。 - 前記仮焼成工程の前に、前記Na含有化合物、前記M含有化合物、前記A含有化合物、及び、前記P含有化合物を粉砕する粉砕工程を含む、請求の範囲第13項に記載のナトリウム電池用正極活物質の製造方法。
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US9660253B2 (en) | 2017-05-23 |
RU2566085C1 (ru) | 2015-10-20 |
CA2846472C (en) | 2016-08-16 |
KR20160025630A (ko) | 2016-03-08 |
CN103765640A (zh) | 2014-04-30 |
KR101795845B1 (ko) | 2017-11-08 |
KR20140041911A (ko) | 2014-04-04 |
AU2012303284A1 (en) | 2014-03-13 |
EP2752925A1 (en) | 2014-07-09 |
BR112014004630A2 (pt) | 2017-03-14 |
JP5673836B2 (ja) | 2015-02-18 |
BR112014004630B1 (pt) | 2021-04-20 |
EP2752925B1 (en) | 2019-01-16 |
CA2846472A1 (en) | 2013-03-07 |
US20140197358A1 (en) | 2014-07-17 |
AU2012303284B2 (en) | 2015-07-23 |
EP2752925A4 (en) | 2015-08-12 |
KR101691774B1 (ko) | 2016-12-30 |
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RU2014106754A (ru) | 2015-10-10 |
CN103765640B (zh) | 2016-11-23 |
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