WO2015037598A1 - 硫化リチウム-鉄-炭素複合体 - Google Patents
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- WO2015037598A1 WO2015037598A1 PCT/JP2014/073871 JP2014073871W WO2015037598A1 WO 2015037598 A1 WO2015037598 A1 WO 2015037598A1 JP 2014073871 W JP2014073871 W JP 2014073871W WO 2015037598 A1 WO2015037598 A1 WO 2015037598A1
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Definitions
- the present invention relates to a lithium sulfide-iron-carbon composite, a production method thereof, and an application thereof.
- lithium ion secondary batteries Due to high performance of portable electronic devices and hybrid vehicles in recent years, secondary batteries (particularly lithium ion secondary batteries) used for them are increasingly required to have higher capacities.
- the increase in capacity of the positive electrode is delayed compared to the negative electrode, and even in the high capacity type Li (Ni, Mn, Co) O 2 materials that have been actively researched and developed recently, the capacity is 250 to 300 mAh. / G or so.
- sulfur has a high theoretical capacity of about 1670 mAh / g and is one of the promising candidates for high-capacity electrode materials.
- sulfur alone does not contain lithium, lithium or an alloy containing lithium must be used for the negative electrode, and there is a drawback that the selection range of the negative electrode is narrow.
- lithium sulfide contains lithium
- alloys such as graphite and silicon can be used for the negative electrode, and the selection range of the negative electrode is drastically expanded, and dendrite generation is caused by using metallic lithium. The risk of short circuits can be avoided.
- lithium sulfide has a problem that it is eluted into the electrolytic solution as lithium polysulfide at the time of charge and discharge, and moves to the negative electrode and segregates (for example, the following non-patent document). 1), it is difficult to express the high capacity inherent in lithium sulfide.
- Patent Literature 1 describes a method in which FeS 2 is compounded with Li 2 S to form a compound such as Li x Fe y S z .
- the introduction of a large amount of different elements increases the formula amount of the electrode active material and decreases the relative Li content, thus reducing the theoretical capacity.
- Patent Document 1 since an equimolar amount of FeS 2 is combined with Li 2 S, the Fe content is 17%, the Li content is 33%, and the theoretical capacity estimated from the contained Li amount is This is about 320 mAh / g, which is significantly lower than the theoretical capacity of lithium sulfide (about 1170 mAh / g). Therefore, it is necessary to suppress the amount of different elements to be added in a small amount for the production of a high-capacity electrode material.
- Non-Patent Document 2 when the Fe content of the Li 2 S—FeS 2 composite is reduced from 16% to 3%, the theoretical capacity increases from about 350 mAh / g to about 930 mAh / g. On the contrary, the capacity obtained when the battery is actually charged / discharged is reduced from about 250 mAh / g to about 3 mAh / g.
- the amount of Fe added to form an Fe—S bond and impart conductivity is considered to be sufficient even if it is about 10% or less.
- the reason for the decrease in the measured capacity is that the added Fe atom is lithium sulfide. This is considered to be due to the fact that the Fe—S bond was not generated by being introduced into the crystal lattice. That is, lithium sulfide itself has hardly changed during the compositing process, and the introduced Fe atom exists as a side reaction product such as Li 2 FeS 2, and therefore does not contribute to an improvement in the utilization rate of the composite. Conceivable.
- the present invention has been made in view of the current state of the prior art described above, and its main object is to use a positive electrode utilization factor in a compound mainly composed of lithium sulfide useful as a positive electrode active material for a lithium secondary battery. It is to provide a novel material having excellent charge / discharge characteristics, which is high, has high capacity, and has good cycle characteristics.
- the present inventors have conducted intensive research to achieve the above-described purpose.
- a mixture containing a lithium-containing compound, an iron-containing compound, and a sulfur-containing compound is filled in a conductive mold, and in a non-oxidizing atmosphere, a direct current pulse current is passed under pressure to conduct current sintering treatment.
- the obtained product is mechanically milled together with the carbon-containing compound after the heat reaction by the lithium sulfide in which the reaction at the atomic level has progressed moderately by the heat reaction during the electric current sintering process.
- a mixture with iron sulfide is formed, and this is mechanically milled with carbon to form a metastable phase in which iron atoms are incorporated into the lithium sulfide crystal lattice. It was found that the phase was stabilized.
- the composite obtained by this method has improved conductivity up to the inside of the crystal due to the presence of iron in the crystal lattice of lithium sulfide, the utilization rate of lithium sulfide is improved, and a high capacity material is obtained. It has been found that the formation of iron bonds significantly reduces free sulfur and improves cycle characteristics.
- the present invention has been completed as a result of further research based on these findings.
- the present invention provides the following lithium sulfide-iron-carbon composite, its production method, and its use.
- Item 1 A composite containing lithium, iron, sulfur and carbon as constituent elements, The crystallite size, which includes lithium sulfide (Li 2 S) as a main phase and is calculated from the half width of the diffraction peak based on the (111) plane of Li 2 S obtained by powder X-ray diffraction, is 50 nm or less.
- a lithium sulfide-iron-carbon composite characterized by: Item 2.
- the Li content is 40 to 60 atomic%
- the Fe content is 2 to 10 atomic%
- the S content is 20 to 40 atomic%
- the C content is 10 to 20 atomic%
- the abundance of the lithium sulfide phase is 90%.
- Item 2. The lithium sulfide-iron-carbon composite according to Item 1, which is at least mol%.
- Item 3. A mixture containing a lithium-containing compound, an iron-containing compound, and a sulfur-containing compound is filled into a conductive mold, and a DC pulse current is applied in a non-oxidizing atmosphere while the mixture is pressurized.
- Item 4. Item 3. A positive electrode active material for a lithium ion secondary battery comprising the lithium sulfide-iron-carbon composite according to Item 1 or 2.
- Item 5. Item 5.
- a lithium ion secondary battery comprising the positive electrode active material according to Item 4.
- An all solid lithium ion secondary battery comprising the positive electrode active material according to Item 4 and a lithium ion conductive solid electrolyte as constituent elements.
- a pretreatment method for a lithium ion secondary battery characterized by increasing in stages and repeating charging and discharging.
- Item 8 Item 7 is characterized in that initial charge / discharge is performed at a capacity of 1/10 to 1/15 of the theoretical capacity of the positive electrode active material, and charge / discharge is performed by gradually increasing the capacity by 30 to 100 mAh / g.
- the pretreatment method of the lithium ion secondary battery as described in 2.
- the lithium sulfide-iron-carbon composite of the present invention is a fine particle having a crystallite size of 50 nm or less, a metastable phase in which iron atoms are introduced into the lithium sulfide crystal lattice is stabilized, and carbon It is a complex in a uniformly dispersed state.
- the iron atoms taken into the lithium sulfide crystal lattice form bonds with sulfur to improve the conductivity to the inside, and the utilization rate is high. High capacity characteristics can be fully exhibited.
- the complex has a sulfur-iron bond, so that elution of polysulfide during Li insertion / desorption reaction is suppressed, and excellent cycle characteristics can be exhibited. As a result, the conductivity is further improved and a high capacity positive electrode active material is obtained.
- the lithium sulfide-iron-carbon composite of the present invention is a highly useful material as a positive electrode active material for lithium secondary batteries such as non-aqueous electrolyte lithium ion secondary batteries and all solid-state lithium ion secondary batteries. It is.
- FIG. 2 is an X-ray diffraction pattern of samples obtained in Examples 1 to 3.
- FIG. 3 is a graph showing charge / discharge characteristics of lithium ion secondary batteries using the samples obtained in Examples 1 to 3 as positive electrode active materials.
- 3 is an X-ray diffraction pattern of samples obtained in Comparative Examples 1 to 3.
- FIG. 6 is a graph showing charge / discharge characteristics of lithium ion secondary batteries using the samples obtained in Comparative Examples 1 to 3 as positive electrode active materials.
- 3 is an X-ray diffraction pattern of samples obtained in Examples 4 and 5.
- FIG. 6 is a graph showing charge / discharge characteristics of lithium ion secondary batteries using the samples obtained in Examples 4 to 6 as positive electrode active materials. 6 is a graph showing charge / discharge characteristics measured in Example 7.
- FIG. 3 is a graph showing charge / discharge characteristics of lithium ion secondary batteries using the samples obtained in Examples 1 to 3 as positive electrode active materials.
- 3 is an X-ray diffraction pattern of samples obtained in Examples 4 and
- the lithium sulfide-iron-carbon composite of the present invention fills a conductive mold with a mixture containing a lithium-containing compound, an iron-containing compound, and a sulfur-containing compound,
- the mixture can be obtained by subjecting the mixture to a heating reaction by applying a direct current pulse current in a non-oxidizing atmosphere under pressure, and then mechanically milling the product together with the carbon-containing compound.
- each of the lithium-containing compound, iron-containing compound, sulfur-containing compound, and carbon-containing compound there are no particular limitations on the type of each of the lithium-containing compound, iron-containing compound, sulfur-containing compound, and carbon-containing compound, and four or more types including one element each of lithium, iron, sulfur, and carbon
- these types of compounds may be mixed and used, or a compound containing two or more elements of lithium, iron, sulfur, and carbon at the same time may be used as part of the raw material.
- raw material compounds are preferably compounds containing no metal element other than lithium and iron. Further, elements other than lithium, iron, sulfur, and carbon contained in the raw material compound are preferably separated and volatilized by heat treatment in a non-oxidizing atmosphere described later.
- lithium sulfide Li 2 S
- lithium carbonate Li 2 CO 3
- lithium hydroxide LiOH
- iron sulfide FeS
- FeS 2 iron sulfate
- FeSO 4 iron sulfate
- carbon-containing compound examples include carbon (C), lithium carbonate (Li 2 CO 3 ), benzothiophene (C 8 H 6 S) and the like.
- iron sulfide (FeS, FeS 2 ), lithium sulfide (Li 2 S) which are composed of only the constituent elements of the product lithium sulfide-iron-carbon complex and can be reacted with a minimum number of raw materials.
- carbon (C) are most preferred.
- graphite, mesoporous carbon, hard carbon (non-graphitizable carbon material) or the like can be used as carbon.
- the shape of these raw material compounds is not particularly limited, but is preferably a powder having an average particle size of about 0.1 to 100 ⁇ m.
- the average particle diameter of the raw material compound is determined by a value at which the cumulative frequency distribution is 50% by particle size distribution measurement by a dry laser diffraction / scattering method.
- the mixing ratio of the raw materials composed of the lithium-containing compound, iron-containing compound, sulfur-containing compound, and carbon-containing compound is not particularly limited, but in the lithium sulfide-iron-carbon composite that is the final product, free sulfur is present.
- an amount is present.
- the Li content in the formed composite is 40 to 60 atomic% (particularly 40 to 55 atomic%), the Fe content is 2 to 10 atomic% (particularly 3 to 8 atomic%), S The content is preferably 20 to 40 atomic% (especially 25 to 35 atomic%), and the C content is preferably 10 to 20 atomic% (especially 13 to 17 atomic%).
- the ratio of each element contained in the raw material compound may be the same as the ratio of each element in the target complex.
- a conductive container is filled with a raw material mixture containing a lithium-containing compound, an iron-containing compound, and a sulfur-containing compound as raw materials, and a pulsed ON-state is applied while being pressurized in a non-oxidizing atmosphere. What is necessary is just to supply an OFF direct current.
- the material of the conductive container is not particularly limited as long as it has conductivity.
- silicon nitride is mixed with carbon and / or iron oxide. What is formed from the mixture etc. can also be used conveniently.
- the electric current sintering step is performed in a non-oxidizing atmosphere, for example, in an inert gas atmosphere such as Ar or N 2 or in a reducing atmosphere such as H 2 . Further, a reduced pressure state in which the oxygen concentration is sufficiently low, for example, a reduced pressure state in which the oxygen partial pressure is about 20 Pa or less may be used.
- the inside of the container may be a non-oxidizing atmosphere.
- the conductive container may not be completely sealed.
- the container is accommodated in the reaction chamber, and the reaction chamber is filled with an inert gas atmosphere.
- a non-oxidizing atmosphere such as a reducing atmosphere may be used.
- the inside of the reaction chamber is preferably an inert gas atmosphere or a reducing gas atmosphere of about 0.1 MPa or more.
- the heating temperature in the electric current sintering process is usually in the temperature range of 400 to 1200 ° C. By making this temperature range, it becomes easy to mutually diffuse each constituent element, and it is in a state of being mixed with each other at the atomic level, and sulfur (free sulfur) that does not bind to transition metals is further reduced, and Li, S, etc. It is possible to obtain a material having a higher capacity by making it difficult to volatilize the element.
- maintain in the above-mentioned heating temperature range it is preferable to set it as about 30 minutes or less, and if it reaches the above-mentioned temperature range, you may stop electricity supply immediately and let it cool. By setting the holding time, elements such as Li and S are less likely to volatilize and a material with a higher capacity can be obtained.
- the pressure at which the raw material powder is pressurized is, for example, about 5 to 60 MPa, preferably about 10 to 50 MPa. By setting the pressure within this range, the contact between the raw material powders can be made stronger, the atomic interdiffusion during heating can be made more sufficient, and the reaction between the atoms in the raw material powder can be made more sufficient.
- the apparatus for conducting the current sintering is not particularly limited as long as the raw material mixture can be heated, cooled, pressurized, and the like and can apply a current necessary for discharge.
- a commercially available electric current sintering apparatus discharge plasma sintering apparatus
- Such an electric current sintering apparatus and its principle are disclosed in, for example, Japanese Patent Laid-Open No. 10-251070.
- FIG. 1 showing a schematic diagram of the electric current sintering apparatus.
- the electric current sintering apparatus 1 has a die (electron conductive container) 3 in which a sample 2 is loaded and a pair of upper and lower electric current punches 4 and 5.
- the energizing punches 4 and 5 are supported by punch electrodes 6 and 7, respectively, and a pulse current is supplied through the punch electrodes 6 and 7 while pressing the sample 2 loaded on the die 3 as necessary. can do.
- the material of the die 3 is not limited, and examples thereof include a carbon material such as graphite.
- the energizing part including the conductive container 3, energizing punches 4 and 5, and punch electrodes 6 and 7 is housed in a water-cooled vacuum chamber 8. Can be adjusted to a predetermined atmosphere. Therefore, the atmosphere control mechanism 15 may be used to adjust the inside of the chamber to a non-oxidizing atmosphere.
- the control device 12 drives and controls the pressurization mechanism 13, the pulse power supply 11, the atmosphere control mechanism 15, the water cooling mechanisms 10 and 16, and the temperature measurement device 17.
- the control device 12 is configured to drive the pressurizing mechanism 13 so that the punch electrodes 6 and 7 pressurize the raw material mixture at a predetermined pressure.
- the pulse current applied for heating for example, a pulsed ON-OFF direct current having a pulse width of about 2 to 3 milliseconds and a period of about 3 Hz to 300 Hz can be used.
- the specific current value varies depending on the type and size of the conductive container, the specific current value may be determined so as to be within the above temperature range. For example, when a graphite mold with an inner diameter of 15 mm is used, about 200 to 1000 A is preferable, and when a mold with an inner diameter of 100 mm is used, about 1000 to 8000 A is preferable.
- the current value may be controlled so that a predetermined temperature can be managed by increasing or decreasing the current value while monitoring the mold material temperature.
- the raw material mixture filled in the conductive container 3 may be pressurized through the punch electrodes 6 and 7.
- the mechanical milling method is a method in which a raw material is mixed and reacted while mechanical energy is applied. According to this method, a mechanical impact or friction is applied to the raw material and the raw material is mixed. Since each contained compound is vigorously brought into contact and refined, a metastable phase is easily obtained.
- the above-described mechanical milling process can be made fine and stable while forming metastable iron-containing lithium sulfide that is difficult to produce only by heat treatment in the electric current sintering process. Furthermore, favorable electroconductivity can be provided by carbon provision from a carbon-containing compound.
- a ball mill, a vibration mill, a turbo mill, a disk mill or the like can be used, and among these, a vibration mill is preferable.
- the mechanical milling process is performed in a non-oxidizing atmosphere.
- the non-oxidizing atmosphere for example, may be Ar, inert gas atmosphere such as N 2, a reducing atmosphere such as H 2.
- the temperature at the time of performing mechanical milling it is preferable to perform mechanical milling at a temperature of about 200 ° C. or lower in order to prevent the volatilization of sulfur and to easily form a composite having a high content ratio of sulfur. .
- the mechanical milling time is not particularly limited, but as described later, mechanical milling may be performed until the crystallite size of the obtained composite is 50 nm or less.
- Lithium sulfide-iron-carbon composite The lithium sulfide-iron-carbon composite obtained by the method described above has a main phase composed of lithium sulfide in powder X-ray diffraction measurement.
- the abundance of the lithium sulfide phase is not particularly limited, but is preferably about 90 mol% or more based on the entire composite.
- the composite is refined by a mechanical milling method and has a crystallite size of 50 nm or less.
- the crystallite size is a value calculated based on the Scherrer equation from the half-value width of the diffraction peak based on the (111) plane indicating the maximum intensity of the lithium sulfide peak observed as the main phase in the powder X-ray diffraction measurement. It is.
- iron atoms are arranged in the lithium sulfide crystal lattice to form Fe—S bonds, and iron-containing lithium sulfide that is a metastable phase is formed, which is refined by a mechanical milling method.
- iron-containing lithium sulfide which is essentially a metastable phase, is stabilized.
- the iron atom as the additive element is arranged in the lithium sulfide crystal lattice to form an Fe-S bond, and contains almost no free sulfur.
- Li is desorbed and inserted, it does not elute into the electrolyte as lithium polysulfide and does not move or deposit on the negative electrode, and the cycle characteristics are good.
- it contains Fe and C, good conductivity is imparted.
- Fe forms a Fe—S bond in the lithium sulfide crystal lattice, the utilization factor inside the lithium sulfide crystal is improved.
- the material has a high capacity.
- the lithium sulfide-iron-carbon composite obtained by the above-described method may contain a small amount of impurities up to about 10 mol% in addition to the lithium sulfide crystal phase. If present, the effect on the charge / discharge characteristics is limited.
- the lithium sulfide-iron-carbon composite of the present invention is effectively used as a positive electrode active material for lithium batteries such as lithium primary batteries, lithium ion secondary batteries, and metal lithium secondary batteries by utilizing the above-described excellent characteristics. it can.
- the lithium sulfide-iron-carbon composite of the present invention is a material containing lithium in the structure, it is a material that can be charged and discharged from charging, and has excellent cycle characteristics. It is useful as a positive electrode active material for lithium ion secondary batteries.
- the lithium ion secondary battery using the lithium sulfide-iron-carbon composite of the present invention as a positive electrode active material may be a nonaqueous electrolyte lithium ion secondary battery using a nonaqueous solvent electrolyte as an electrolyte, or An all-solid-state lithium ion secondary battery using a lithium ion conductive solid electrolyte may be used.
- the structures of the nonaqueous electrolyte lithium ion secondary battery and the all solid state lithium ion secondary battery are the same as those of known lithium secondary batteries except that the lithium sulfide-iron-carbon composite of the present invention is used as the positive electrode active material. It can be.
- the basic structure of a nonaqueous electrolyte lithium ion secondary battery is the same as that of a known nonaqueous electrolyte lithium ion secondary battery, except that the above-described lithium sulfide-iron-carbon composite is used as a positive electrode active material. It may be the same.
- a positive electrode current collector such as Al, Ni, stainless steel, carbon cloth, etc. prepared by mixing the above-described lithium sulfide-iron-carbon composite as a positive electrode active material and mixing a conductive agent and a binder. What is necessary is just to make it carry on.
- the conductive agent for example, carbon materials such as graphite, cokes, carbon black, and acicular carbon can be used.
- both materials containing lithium and materials not containing lithium can be used.
- materials containing lithium and materials not containing lithium can be used.
- hardly sinterable carbon, lithium metal, etc., tin, silicon, alloys containing these, SiO, and the like can also be used.
- These negative electrode active materials may also be supported on a negative electrode current collector made of Al, Cu, Ni, stainless steel, carbon, or the like using a conductive agent, a binder, or the like, if necessary.
- the separator is made of, for example, a polyolefin resin such as polyethylene or polypropylene, a fluororesin, nylon, aromatic aramid, inorganic glass, or the like, and a material such as a porous film, a nonwoven fabric, or a woven fabric can be used.
- solvents for the nonaqueous electrolyte known solvents can be used as solvents for nonaqueous solvent secondary batteries such as carbonates, ethers, nitriles, and sulfur-containing compounds.
- the all-solid-state lithium ion secondary battery has the same structure as a known all-solid-state lithium ion secondary battery except that the lithium sulfide-iron-carbon composite of the present invention is used as a positive electrode active material. Good.
- a polymer solid electrolyte such as a polyethylene oxide polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain and a polyoxyalkylene chain, a sulfide solid electrolyte, an oxidation
- a physical solid electrolyte or the like can be used as the electrolyte.
- the lithium sulfide-iron-carbon composite of the present invention is used as a positive electrode active material, and a positive electrode mixture containing a conductive agent, a binder, and a solid electrolyte is Ti, Al, What is necessary is just to carry
- the conductive agent for example, a carbon material such as graphite, cokes, carbon black, and acicular carbon can be used as in the case of the non-aqueous solvent secondary battery.
- the shape of the non-aqueous electrolyte lithium ion secondary battery and the all solid state lithium ion secondary battery is not particularly limited, and may be any of a cylindrical shape, a rectangular shape, and the like.
- the lithium sulfide-iron-carbon composite of the present invention is used as a positive electrode active material of a lithium secondary battery such as a non-aqueous electrolyte lithium ion secondary battery or an all-solid-state lithium ion secondary battery, It is preferable to charge / discharge preliminarily at a capacity lower than the theoretical capacity, and repeatedly increase / decrease the capacity in stages, after the battery having the structure as described above is prepared.
- a lithium secondary battery such as a non-aqueous electrolyte lithium ion secondary battery or an all-solid-state lithium ion secondary battery
- Li is desorbed and inserted step by step, and the structural change accompanying it, that is, rearrangement of each constituent atom is stepped.
- the Li is smoothly desorbed and inserted, and shows better charge / discharge characteristics than the composite immediately after obtained by the mechanical milling method.
- Preliminary charging / discharging conditions are not particularly limited.
- the initial charging / discharging is performed at a capacity of about 1/10 to 1/15 of the theoretical capacity, and then the capacity is about 30 to 100 mAh / g.
- Charging / discharging is performed by increasing the capacity, and the capacity is sequentially increased by about 30 to 100 mAh / g, and charging / discharging may be continued until the capacity value does not increase any more.
- the potential range is not particularly limited.
- the potential range may be in the range of a lower limit voltage of 1.0 to 1.3 V and an upper limit voltage of 2.8 to 3.0 V, as in the case of a normal sulfide electrode material.
- the lithium sulfide-iron-carbon composite in which iron is arranged in the lithium sulfide crystal lattice, which is originally a metastable structure can be further stabilized.
- Charge / discharge characteristics such as capacity and cycle characteristics can be further improved.
- Example 1 Commercially available lithium sulfide (Li 2 S) (average particle size of about 16 [mu] m) and iron sulfide (FeS 2) (average particle size of about 6 [mu] m), the molar ratio of 3: To the 1, a glove box under an argon gas atmosphere ( (Dew point ⁇ 80 ° C.), thoroughly mixed in a mortar, and filled into a graphite mold having an inner diameter of 15 mm.
- Li 2 S lithium sulfide
- FeS 2 iron sulfide
- the graphite mold filled with the raw material was accommodated in an electric current sintering machine.
- the energized part including the graphite mold and the electrode part is accommodated in a vacuum chamber. After the vacuum (about 20 Pa) is deaerated in the chamber, high-purity argon gas (oxygen concentration: about 0.2 ppm) is brought to atmospheric pressure. Filled.
- a pulse current of about 600 A (pulse width 2.5 milliseconds, period 28.6 Hz) was applied while pressurizing the raw material filled in the graphite mold at about 30 MPa.
- the vicinity of the graphite mold was heated at a temperature increase rate of about 200 ° C./min, and reached 600 ° C. 3 minutes after the start of pulse current application.
- the current application and pressurization were stopped and the mixture was allowed to cool naturally.
- the graphite jig was transferred to a glove box with an argon gas atmosphere having a dew point of ⁇ 80 ° C., and the reaction product of lithium sulfide and iron sulfide was taken out of the mold and pulverized in a mortar.
- a vibration cup mill model MC-4A manufactured by Ito Seisakusho, the material was treated for 8 hours by the mechanical milling method.
- the ratio (atomic%) of each element used for the raw material was Li41.7%, Fe7.0%, S34.8%, C16.5%.
- the X-ray diffraction pattern of the obtained sample is shown in FIG.
- a peak derived from lithium sulfide was observed as the main phase, and an FeS peak was observed as a small amount of impurities.
- the abundance ratio (mol%) of FeS estimated by Rietveld analysis was about 9%.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 25 nm. From these results, it was confirmed that a lithium sulfide-iron-carbon composite having a main phase of lithium sulfide and a crystallite size of 50 nm or less could be produced by the method described above.
- the charge / discharge characteristics are as shown in FIG. 3.
- the initial charge capacity is about 510 mAh / g
- the initial discharge capacity is about 660 mAh / g
- the value in the case of the sample measured in Comparative Example 1 described later (initial charge capacity is about 370 mAh).
- / G an initial discharge capacity of about 490 mA / g)
- a remarkably high charge / discharge capacity was exhibited.
- the discharge capacity after 5 cycles was about 450 mAh / g (capacity maintenance rate of about 68%), which was higher than the value in Comparative Example 1 (about 300 mAh / g, about 60%) described later.
- a high-capacity electrode material can be obtained by producing a lithium sulfide-iron-carbon composite by the method described above.
- Comparative Example 1 After mixing commercially available lithium sulfide (Li 2 S) (average particle size of about 16 ⁇ m) and iron sulfide (FeS 2 ) (average particle size of about 6 ⁇ m) so that the molar ratio is 3: 1, the same conditions as in Example 1 Then, it was treated at 600 ° C. by an electric current sintering method.
- Li 2 S lithium sulfide
- FeS 2 iron sulfide
- the ratio (atomic%) of each element used for the raw materials was Li 41.7%, Fe 7.0%, S 34.8%, and C 16.5%, exactly as in Example 1.
- the X-ray diffraction pattern of the obtained sample is shown in FIG.
- the product is mainly composed of Li 2.33 Fe 0.67 S 2 , Li 2 FeS 2 , and Li 2 S, and the main phase is Li 2.33 Fe 0.67 S 2 . there were.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 110 nm.
- lithium sulfide is the main phase. It was found that a lithium sulfide-iron-carbon composite having a crystallite size of 50 nm or less could not be obtained.
- Example 1 A charge / discharge test was performed in the same manner as in Example 1 except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 5.
- the initial charge capacity was about 370 mAh / g
- the initial discharge capacity was about 490 mAh / g
- the composite obtained in Example 1 (initial charge capacity about 510 mAh / g, initial Compared with the discharge capacity of about 660 mAh / g), the value was extremely low.
- the discharge capacity after 5 cycles was about 300 mAh / g (capacity maintenance rate about 60%), which was lower than the value in Example 1 (about 450 mAh / g, about 68%).
- the X-ray diffraction pattern of the obtained sample is shown in FIG.
- 10% or more of an impurity phase other than Li 2 S was contained.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 22 nm.
- Example 1 A charge / discharge test was performed in the same manner as in Example 1 except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 5.
- the initial charge capacity was about 470 mAh / g
- the initial discharge capacity was about 690 mAh / g
- the composite obtained in Example 1 initial charge capacity about 510 mAh / g, initial Although the discharge capacity was about 660 mAh / g)
- the discharge capacity after 5 cycles was about 190 mAh / g (capacity maintenance rate of about 27%).
- Example 1 about 450 mAh / g, about 68%. This is because high-temperature heat treatment by electric sintering is not performed, so mixing of each element at the atomic level is insufficient, and sulfur (free sulfur) not bonded to the transition metal increases and cycle characteristics deteriorate. It is thought that it was because.
- Example 2 A lithium sulfide-iron-carbon composite was produced in the same manner as in Example 1 except that the mixing ratio of lithium sulfide (Li 2 S) and iron sulfide (FeS 2 ) was 4: 1 in terms of molar ratio.
- the ratio (atomic%) of each element used for the raw materials was Li 44.9%, Fe 5.6%, S 33.7%, and C 15.8%.
- the X-ray diffraction pattern of the obtained sample is shown in FIG.
- a peak derived from lithium sulfide was recognized as the main phase, and an FeS peak was recognized as a very small amount of impurities.
- the abundance ratio (mol%) of FeS estimated by Rietveld analysis was about 5%.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 29 nm.
- charge / discharge is performed at a capacity of 50 mAh / g, then, the capacity is increased by 50 mAh / g, and charge / discharge is performed at a capacity of 100 mAh / g. While increasing the capacity stepwise by 50 mAh / g, charging and discharging were performed until the total capacity reached 600 mAh / g.
- the electrode after this pre-charge / discharge treatment was taken out and subjected to X-ray diffraction measurement, only a broad peak of Li 2 S was observed, and the composite was mainly composed of lithium sulfide even after the pre-treatment. I understood that.
- the charge / discharge characteristics are as shown in FIG. 3, the initial charge capacity is about 540 mAh / g, the initial discharge capacity is about 650 mAh / g, and the value in the case of the sample measured in Example 1 (initial charge capacity about 510 mAh / g).
- the initial charge capacity was about 660 mA / g), which was a high charge / discharge capacity.
- the discharge capacity after 5 cycles was about 600 mAh / g (capacity maintenance rate about 93%), which was higher than the value in Example 1 (about 450 mAh / g, about 68%).
- Example 3 A lithium sulfide-iron-carbon composite was produced in exactly the same manner as in Example 1, except that the mixing ratio of lithium sulfide (Li 2 S) and iron sulfide (FeS 2 ) was 5: 1 in molar ratio. The ratio (atomic%) of each element used for the raw materials was Li 47.1%, Fe 4.7%, S 33.0%, and C 15.2%.
- the X-ray diffraction pattern of the obtained sample is shown in FIG. As is apparent from FIG. 2, it was found to consist of diffraction peaks of only lithium sulfide.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 27 nm.
- Example 2 A charge / discharge test was performed in exactly the same manner as in Example 2 including the preliminary charge / discharge treatment, except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 3, the initial charge capacity is about 560 mAh / g, the initial discharge capacity is about 600 mAh / g, and the value in the case of the sample measured in Example 1 (initial charge capacity about 510 mAh / g).
- the initial charge capacity was about 660 mA / g), which was a high charge / discharge capacity.
- the discharge capacity after 5 cycles was about 450 mAh / g (capacity maintenance rate of about 75%), which was about the same value as that in Example 1 (about 450 mAh / g, about 68%).
- a high-capacity electrode material can be obtained by producing a lithium sulfide-iron-carbon composite by the method described above.
- Comparative Example 3 Commercially available lithium sulfide (Li 2 S) (average particle size of about 16 ⁇ m) and iron sulfide (FeS 2 ) (average particle size of about 6 ⁇ m) were mixed so that the molar ratio was 5: 1, and then the same conditions as in Example 3 Then, current sintering was performed at 600 ° C.
- Li 2 S lithium sulfide
- FeS 2 iron sulfide
- the ratio (atomic%) of each element used as the raw material was Li 47.1%, Fe 4.7%, S 33.0%, and C 15.2%, exactly as in Example 3.
- the X-ray diffraction pattern of the obtained sample is shown in FIG. As is clear from FIG. 4, this product has a peak derived from lithium sulfide as the main phase, and other peaks that can be attributed to Li 2.33 Fe 0.67 S 2 and Li 2 FeS 2 . .
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 120 nm.
- Example 3 A charge / discharge test was performed in the same manner as in Example 1 except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 5, and the initial charge capacity is about 270 mAh / g and the initial discharge capacity is about 330 mAh / g.
- the value was extremely low.
- the discharge capacity after 5 cycles was also about 180 mAh / g (capacity maintenance rate about 55%), which was lower than the value in Example 1 (about 450 mAh / g, about 68%).
- Example 4 A lithium sulfide-iron-carbon composite was produced in exactly the same manner as in Example 1 except that the iron-containing compound used as a raw material was iron sulfide (FeS) (average particle size of about 8 ⁇ m). The ratio (atomic%) of each element used for the raw materials was Li 45.8%, Fe 7.6%, S 30.6%, and C 16.0%.
- FeS iron sulfide
- the X-ray diffraction pattern of the obtained sample is shown in FIG.
- the main phase consists of a diffraction peak of lithium sulfide.
- the abundance ratio (mol%) of Li 2 S estimated by Rietveld analysis was about 99%.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 25 nm.
- Example 2 A charge / discharge test was performed in exactly the same manner as in Example 2 including the preliminary charge / discharge treatment, except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 7, the initial charge capacity is about 630 mAh / g, the initial discharge capacity is about 680 mAh / g, and the value in the case of the sample measured in Example 1 (initial charge capacity about 510 mAh / g).
- the initial charge capacity was about 660 mA / g), which was a high charge / discharge capacity.
- the discharge capacity after 5 cycles was about 550 mAh / g (capacity maintenance rate of about 81%), which was higher than the value in Example 1 (about 450 mAh / g, about 68%).
- Example 5 A lithium sulfide-iron-carbon composite was produced in exactly the same manner as in Example 4 except that the mixing ratio of lithium sulfide (Li 2 S) and iron sulfide (FeS) was 4: 1 in molar ratio.
- the ratio (atomic%) of each element used for the raw materials was Li 48.4%, Fe 6.1%, S30.3%, and C15.2%.
- the X-ray diffraction pattern of the obtained sample is shown in FIG. As apparent from FIG. 6, it was found to consist only of the diffraction peak of lithium sulfide.
- the crystallite size estimated from the half width of the diffraction peak based on the (111) plane of lithium sulfide was about 28 nm.
- a charge / discharge test was performed in exactly the same manner as in Example 2 including the preliminary charge / discharge treatment, except that this composite powder was used as a positive electrode material for a lithium secondary battery.
- the charge / discharge characteristics are as shown in FIG. 7.
- the initial charge capacity is about 570 mAh / g
- the initial discharge capacity is about 730 mAh / g
- the value in the case of the sample measured in Example 4 (initial charge capacity about 630 mAh / g).
- the initial charge capacity was about 680 mA / g), which was a high charge / discharge capacity.
- the discharge capacity after 5 cycles was about 650 mAh / g (capacity maintenance rate about 90%), which was higher than the value in Example 4 (about 550 mAh / g, about 81%).
- Example 6 An all-solid battery was assembled using the lithium sulfide-iron-carbon composite obtained in Example 5 as the positive electrode material, indium metal as the negative electrode, and 75Li 2 S-25P 2 S 5 as the electrolyte, and a charge / discharge test was conducted. It was.
- the positive electrode As for the positive electrode, the above-described lithium sulfide-iron-carbon composite and 75Li 2 S-25P 2 S 5 electrolyte were mixed at a weight ratio of 7: 3 and used as the positive electrode mixture. Positive electrode mixture / 75Li 2 S-25P 2 pellets were produced battery 10mm diameter by pressure molding the S 5 electrolyte / indium foil. This was subjected to a charge / discharge test at the start of charging by constant current measurement at a current density of 11.7 mA / g (74 ⁇ A / cm 2 ) at a cutoff of 0.4 to 3.0 V.
- the charge / discharge characteristics are as shown in FIG. 7.
- the initial charge capacity is about 560 mAh / g
- the initial discharge capacity is about 450 mAh / g
- the discharge capacity after 5 cycles is about 390 mAh / g (capacity maintenance ratio is about 87). %)
- Capacity maintenance ratio is about 87).
- Example 7 Except for using the lithium sulfide-iron-carbon composite obtained in Example 3 as the positive electrode material and setting the potential range to the lower limit voltage of 1.8 V and the upper limit voltage of 2.6 V, the preliminary charge / discharge treatment was performed.
- a charge / discharge test was conducted in exactly the same manner as in Example 3.
- the charge / discharge characteristics are as shown in FIG. 8, the initial charge capacity is about 620 mAh / g, the initial discharge capacity is about 600 mAh / g, and the value in the case of the sample measured in Example 3 (initial charge capacity about 560 mAh / g).
- the initial charge capacity was about 600 mA / g), which was a high charge / discharge capacity.
- the discharge capacity after 5 cycles was about 490 mAh / g (capacity maintenance rate of about 81%), which was higher than the value in Example 3 (about 450 mAh / g, about 75%).
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Abstract
Description
項1.リチウム、鉄、硫黄及び炭素を構成元素として含む複合体であって、
硫化リチウム(Li2S)を主相として含み、粉末X線回折によって得られたLi2Sの(111)面に基づく回折ピークの半価幅から算出される結晶子サイズが50nm以下であることを特徴とする、硫化リチウム-鉄-炭素複合体。
項2.Li含有量が40~60原子%、Fe含有量が2~10原子%、S含有量が20~40原子%、C含有量が10~20原子%であり、硫化リチウム相の存在量が90モル%以上である、項1に記載の硫化リチウム-鉄-炭素複合体。
項3.リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において、該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、得られた生成物を炭素含有化合物と共にメカニカルミリング処理することを特徴とする、項1に記載の硫化リチウム-鉄-炭素複合体の製造方法。
項4.項1又は2に記載の硫化リチウム-鉄-炭素複合体を含むリチウムイオン二次電池用正極活物質。
項5.項4に記載の正極活物質を構成要素とするリチウムイオン二次電池。
項6.項4に記載の正極活物質とリチウムイオン伝導性固体電解質を構成要素として含む全固体リチウムイオン二次電池。
項7.項1又は2に記載の硫化リチウム-鉄-炭素複合体を正極活物質として含むリチウムイオン二次電池を形成した後、正極活物質の理論容量より低い容量で充放電を行い、次いで、容量を段階的に増加して、充放電を繰り返すことを特徴とする、リチウムイオン二次電池の前処理方法。
項8.最初の充放電を正極活物質の理論容量の1/10~1/15の容量で行い、容量を30~100mAh/gずつ段階的に増加させて充放電を行うことを特徴とする、項7に記載のリチウムイオン二次電池の前処理方法。
項9.電位範囲が、下限電圧1.0~1.3V、上限電圧2.8~3.0Vの範囲内で行うことを特徴とする、項7又は8に記載のリチウムイオン二次電池の前処理方法。
本発明の硫化リチウム-鉄-炭素複合体は、リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、生成物を炭素含有化合物と共にメカニカルミリング処理することによって得ることができる。この方法によれば、加熱反応によって原子レベルでの反応が適度に進行した硫化リチウムと硫化鉄の混合物を得ることができ、これを炭素と共にメカニカルミリング処理することによって、粒子が微細化されて、鉄原子が硫化リチウム相内に取り込まれた準安定相が安定化され、更に、炭素が均一に分散した状態の複合体を得ることができる。以下、この方法について具体的に説明する。
本発明では、原料として、リチウム含有化合物、鉄含有化合物、硫黄含有化合物、及び炭素含有化合物を用いる。
(i)通電焼結工程
本発明では、まず、通電焼結工程として、リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において該混合物を加圧した状態で、放電プラズマ焼結法、パルス通電焼結法、プラズマ活性化焼結法等と呼ばれる直流パルス電流を通電する方法で各化合物を加熱反応させる。原料として用いる炭素含有化合物は、この段階で添加してもよく、後述するメカニカルミリング処理の際に添加してもよい。この方法によれば、通電焼結工程における熱処理により、各元素が拡散移動し、原子レベルで相互に混合した状態の中間体を作製することが出来る。
上記した通電焼結工程で得られた生成物を炭素含有化合物と共にメカニカルミリング処理して、混合、粉砕及び反応させることによって、本発明の目的とする硫化リチウム-鉄-炭素複合体を得ることができる。通電焼結工程で用いた原料に、所定量の炭素含有化合物が含まれていない場合には、メカニカルミリング工程の前に、炭素含有化合物を加えればよい。
上記した方法で得られる硫化リチウム-鉄-炭素複合体は、粉末X線回折測定において、主相が硫化リチウムからなるものである。硫化リチウム相の存在量は特に限定的ではないが、該複合体全体を基準として90モル%程度以上であることが好ましい。
本発明の硫化リチウム-鉄-炭素複合体を、非水電解質リチウムイオン二次電池、全固体型リチウムイオン二次電池等のリチウム二次電池の正極活物質として用いる場合には、目的とする構造の電池を作成した後、予備的に、理論容量より低い容量で充放電を行い、段階的に容量を増加させて充放電を繰り返し行うことが好ましい。この方法によれば、本発明の硫化リチウム-鉄-炭素複合体は、Liの脱離・挿入を少量ずつ段階的に行われ、それに伴う構造的な変化、すなわち各構成原子の再配列が段階的に大きくなることで、Liの脱離・挿入がスムーズになり、メカニカルミリング法によって得られた直後の複合体よりも良好な充放電特性を示す。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう、アルゴンガス雰囲気のグローブボックス内(露点-80℃)で秤量し、乳鉢で充分に混合後、内径15mmの黒鉛型材に充填した。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう混合後、実施例1と同じ条件で通電焼結法で600℃処理した。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう秤量後、更にアセチレンブラック(AB)粉末を、硫化リチウム+硫化鉄の混合粉:AB=9:1の重量比となるよう混合し、実施例1と同様の条件でメカニカルミリング法により8時間処理して複合体を作製した。原料に用いた各元素の比率(原子%)は、実施例1と全く同様、Li41.7%、Fe7.0%、S34.8%、C16.5%であった。
硫化リチウム(Li2S)と硫化鉄(FeS2)の混合比を、モル比で4:1とすること以外は実施例1と全く同様にして硫化リチウム-鉄-炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li44.9%、Fe5.6%、S33.7%、C15.8%であった。
硫化リチウム(Li2S)と硫化鉄(FeS2)の混合比を、モル比で5:1とすること以外は実施例1と全く同様にして硫化リチウム-鉄-炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li47.1%、Fe4.7%、S33.0%、C15.2%であった。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が5:1となるよう混合後、実施例3と同じ条件で600℃で通電焼結を行った。
原料として用いた鉄含有化合物を硫化鉄(FeS)(平均粒径約8μm)とする以外は実施例1と全く同様にして硫化リチウム-鉄-炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li45.8%、Fe7.6%、S30.6%、C16.0%であった。
硫化リチウム(Li2S)と硫化鉄(FeS)の混合比を、モル比で4:1とすること以外は実施例4と全く同様にして硫化リチウム-鉄-炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li48.4%、Fe6.1%、S30.3%、C15.2%であった。
実施例5で得られた硫化リチウム-鉄-炭素複合体を正極材料に用い、負極にインジウム金属、電解質に75Li2S-25P2S5を用いて全固体電池を組み上げ、充放電試験を行った。
実施例3で得られた硫化リチウム-鉄-炭素複合体を正極材料に用い、電位範囲を下限電圧1.8V、上限電圧2.6Vにすること以外は、予備的充放電処理を含めて実施例3と全く同様にして充放電試験を行った。充放電特性は図8に示す通りであり、初期充電容量は約620mAh/g、初期放電容量は約600mAh/gとなり、実施例3で測定した試料の場合の値(初期充電容量約560mAh/g、初期放電容量約600mA/g)と同程度の高い充放電容量を示した。また、5サイクル後の放電容量は約490mAh/g(容量維持率約81%)となり、実施例3での値(約450mAh/g、約75%)よりも高い値を示した。
2 試料
3 ダイ(導電性容器)
4、5 通電用パンチ
6,7 パンチ電極
8 水冷真空チャンバー
9 冷却水路
10、16 水冷却機構
11 焼結用電源
12 制御装置
13 加圧機構
14 位置計測機構
15 雰囲気制御機構
17 温度計測装置
Claims (9)
- リチウム、鉄、硫黄及び炭素を構成元素として含む複合体であって、
硫化リチウム(Li2S)を主相として含み、粉末X線回折によって得られたLi2Sの(111)面に基づく回折ピークの半価幅から算出される結晶子サイズが50nm以下であることを特徴とする、硫化リチウム-鉄-炭素複合体。 - Li含有量が40~60原子%、Fe含有量が2~10原子%、S含有量が20~40原子%、C含有量が10~20原子%であり、硫化リチウム相の存在量が90モル%以上である、請求項1に記載の硫化リチウム-鉄-炭素複合体。
- リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において、該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、得られた生成物を炭素含有化合物と共にメカニカルミリング処理することを特徴とする、請求項1に記載の硫化リチウム-鉄-炭素複合体の製造方法。
- 請求項1又は2に記載の硫化リチウム-鉄-炭素複合体を含むリチウムイオン二次電池用正極活物質。
- 請求項4に記載の正極活物質を構成要素とするリチウムイオン二次電池。
- 請求項4に記載の正極活物質とリチウムイオン伝導性固体電解質を構成要素として含む全固体リチウムイオン二次電池。
- 請求項1又は2に記載の硫化リチウム-鉄-炭素複合体を正極活物質として含むリチウムイオン二次電池を形成した後、正極活物質の理論容量より低い容量で充放電を行い、次いで、容量を段階的に増加して、充放電を繰り返すことを特徴とする、リチウムイオン二次電池の前処理方法。
- 最初の充放電を正極活物質の理論容量の1/10~1/15の容量で行い、容量を30~100mAh/gずつ段階的に増加させて充放電を行うことを特徴とする、請求項7に記載のリチウムイオン二次電池の前処理方法。
- 電位範囲が、下限電圧1.0~1.3V、上限電圧2.8~3.0Vの範囲内で行うことを特徴とする、請求項7又は8に記載のリチウムイオン二次電池の前処理方法。
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