WO2020202602A1 - 全固体リチウムイオン電池用酸化物系正極活物質、全固体リチウムイオン電池用酸化物系正極活物質の前駆体の製造方法、全固体リチウムイオン電池用酸化物系正極活物質の製造方法及び全固体リチウムイオン電池 - Google Patents
全固体リチウムイオン電池用酸化物系正極活物質、全固体リチウムイオン電池用酸化物系正極活物質の前駆体の製造方法、全固体リチウムイオン電池用酸化物系正極活物質の製造方法及び全固体リチウムイオン電池 Download PDFInfo
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Definitions
- the present invention relates to an oxide-based positive electrode active material for an all-solid lithium-ion battery, a method for producing a precursor of an oxide-based positive electrode active material for an all-solid lithium-ion battery, and a production of an oxide-based positive electrode active material for an all-solid lithium-ion battery. Methods and all-solid-state lithium-ion batteries.
- lithium batteries are attracting attention from the viewpoint of high energy density. Further, high energy density and improvement of battery characteristics are also required for lithium secondary batteries in large-scale applications such as power sources for automobiles and road leveling.
- the positive electrode active material of the non-aqueous electrolyte secondary battery includes lithium cobalt composite oxide represented by lithium cobalt oxide (LiCoO 2 ) and lithium nickel composite oxide represented by lithium nickel oxide (LiNiO 2 ). Lithium-manganese composite oxides such as lithium manganate (LiMnO 2 ) are widely used.
- lithium cobalt oxide has a problem that it is expensive because the reserves of cobalt are small, and contains cobalt as a main component, which has unstable supply and large price fluctuations. Therefore, a lithium nickel composite oxide or a lithium manganese composite oxide containing relatively inexpensive nickel or manganese as a main component has attracted attention from the viewpoint of cost (Patent Documents 1 to 3).
- Patent Documents 1 to 3 Although lithium manganate is superior to lithium cobalt oxide in thermal stability, its charge / discharge capacity is much smaller than that of other materials, and its charge / discharge cycle characteristics indicating its life are also very short.
- lithium nickel oxide is expected to be a positive electrode active material capable of producing a battery having a high energy density at low cost because it exhibits a larger charge / discharge capacity than lithium cobalt oxide.
- An all-solid-state battery that does not use a non-aqueous electrolyte solution that may ignite, leak, or explode improves safety, but cannot make good contact between the solid electrolyte and the positive electrode active material in the positive electrode layer.
- Battery performance may deteriorate. For example, when the electrical contact state is insufficient at the interface between the solid electrolyte and the positive electrode active material, the internal resistance of the battery increases and the battery performance deteriorates such that sufficient capacity for functioning as a battery cannot be secured. May be invited. Therefore, in order to improve the contact between the solid electrolyte and the positive electrode active material, it is conceivable to increase the contact points by reducing the particle size of each particle. However, there is a problem that the tap density is lowered by reducing the particle size of the positive electrode active material, and the energy density per volume is lowered.
- an object of the present embodiment of the present invention to provide an oxide-based positive electrode active material for an all-solid-state lithium-ion battery, which can obtain excellent battery characteristics when used in an all-solid-state lithium-ion battery.
- the composition formula is Li a Ni x Co y Mn 1-xy O 2 (In the formula, 0.98 ⁇ a ⁇ 1.05, 0.8 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 0.20.) All-solid-state lithium ion having an average particle size D50 of 1.0 to 5.0 ⁇ m, a tap density of 1.6 to 2.5 g / cc, and a circularity of 0.85 to 0.95. It is an oxide-based positive electrode active material for batteries.
- an aqueous solution containing a basic aqueous solution of a nickel salt, a cobalt salt, a manganese salt, an aqueous ammonia and an alkali metal is used as a reaction solution, and the pH in the reaction solution is 10.5 to 11 .5, the ammonium ion concentration 5 ⁇ 25 g / L, comprising the step of performing crystallization reaction while controlling the liquid temperature at 50 ⁇ 65 °C, Ni x Co y Mn 1-xy formula is complex hydroxide (OH) 2 (in the formula, 0.8 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 0.20), the average particle diameter D50 is 1.0 to 5.0 ⁇ m, and the circularity Is a method for producing a precursor of an oxide-based positive electrode active material for an all-solid lithium-ion battery having a pH of 0.85 to 0.95.
- the reaction solution in the crystallization reaction, is subjected to a stirring required power per unit volume in the reaction vessel.
- the reaction is carried out by stirring at 1.8 to 7.3 kW / m 3 .
- the precursor produced by the method for producing a precursor of an oxide-based positive electrode active material for an all-solid-state lithium-ion battery of the present invention is made of a metal composed of Ni, Co and Mn.
- This is a method for producing an oxide-based positive electrode active material for an all-solid-state lithium-ion battery which comprises a step of firing at 450 to 520 ° C. for 2 to 15 hours and then further firing at 680 to 850 ° C. for 2 to 15 hours.
- the present invention includes an all-solid-state lithium ion having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer, and the oxide-based positive electrode active material for an all-solid-state lithium-ion battery of the present invention is provided in the positive electrode layer. It is a battery.
- an oxide-based positive electrode active material for an all-solid-state lithium-ion battery which can obtain excellent battery characteristics when used in an all-solid-state lithium-ion battery.
- composition of oxide-based positive electrode active material for all-solid-state lithium-ion batteries All-solid-state lithium-ion oxide-based positive electrode active material for a battery according to an embodiment of the present invention, the composition formula Li a Ni x Co y Mn 1 -xy O 2 (In the formula, 0.98 ⁇ a ⁇ 1.05, 0.8 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 0.20.) It is represented by.
- the amount of lithium is insufficient and it is difficult to maintain a stable crystal structure. If it exceeds, the discharge capacity of the all-solid-state lithium-ion battery produced by using the positive electrode active material may decrease.
- the average particle size D50 of the oxide-based positive electrode active material for an all-solid-state lithium-ion battery according to the embodiment of the present invention is controlled to 1.0 to 5.0 ⁇ m. According to such a configuration, the contact area between the solid electrolyte and the positive electrode active material becomes large, and the conductivity of Li ions between the positive electrode active material and the solid electrolyte becomes good.
- the average particle size D50 may be 1.5 ⁇ m or more, 2.5 ⁇ m or more, or 3.0 ⁇ m or more. Further, the average particle diameter D50 may be 5.0 ⁇ m or less, 4.5 ⁇ m or less, or 3.5 ⁇ m or less.
- the tap density of the oxide-based positive electrode active material for an all-solid-state lithium-ion battery according to the embodiment of the present invention is controlled to 1.6 to 2.5 g / cc. According to such a configuration, when used in an all-solid-state lithium-ion battery, the energy density increases per volume of the oxide-based positive electrode active material for the all-solid-state lithium-ion battery, resulting in excellent battery capacity and battery capacity retention rate. Is obtained.
- the tap density is preferably 1.8 to 2.5 g / cc, more preferably 2.0 to 2.5 g / cc.
- the circularity of the oxide-based positive electrode active material for an all-solid-state lithium-ion battery according to the embodiment of the present invention is controlled to 0.85 to 0.95.
- the tap density can be controlled to 1.6 to 2.5 g / cc even though the average particle size D50 is as small as 1.0 to 5.0 ⁇ m.
- the contact area between the solid electrolyte and the positive electrode active material is increased, and the conductivity of Li ions between the positive electrode active material and the solid electrolyte is improved, while the energy density per volume is large for all-solid lithium-ion batteries.
- An oxide-based positive electrode active material can be provided.
- Precursor of all solid oxide-based positive electrode active material for a lithium ion battery in the composition formula is complex hydroxide Ni x Co y Mn 1-xy (OH) 2 (wherein, 0 It is represented by (8 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 0.20).
- the average particle size D50 of the precursor is 1.0 to 5.0 ⁇ m, and the circularity is 0.85 to 0.95.
- the method for producing a precursor of an oxide-based positive electrode active material for an all-solid lithium-ion battery is to use an aqueous solution containing a basic aqueous solution of a nickel salt, a cobalt salt, a manganese salt, an aqueous ammonia and an alkali metal.
- the reaction solution comprises a step of performing a crystallization reaction while controlling the pH in the reaction solution to 10.5 to 11.5, the ammonium ion concentration to 5 to 25 g / L, and the liquid temperature to 50 to 65 ° C.
- the method for producing a precursor of an oxide-based positive electrode active material for an all-solid-state lithium-ion battery thus controls the pH, ammonium ion concentration, and liquid temperature in the reaction solution within a certain range. However, it is characterized by a crystallization reaction, and by this method, an oxide for an all-solid-state lithium-ion battery having an average particle diameter D50 of 1.0 to 5.0 ⁇ m and a circularity of 0.85 to 0.95.
- a precursor of the system positive electrode active material can be prepared.
- the pH, ammonium ion concentration, and liquid temperature in the reaction solution are kept within a certain range as described above.
- the crystallization reaction is carried out under control, and for that purpose, for example, three raw materials of (1) a mixed aqueous solution of a nickel salt, a cobalt salt and a manganese salt, (2) an aqueous ammonia solution and (3) a basic aqueous solution of an alkali metal are used. , Continuously supply small amounts to the reaction tank at the same time to react.
- a mixed aqueous solution of nickel salt, cobalt salt, and manganese salt is 0.60 L / h
- (2) aqueous ammonia is 0.40 L / h
- (3) water in a 10 L reaction vessel An aqueous solution of sodium oxide may be continuously supplied at 0.35 L / h at the same time for a crystallization reaction.
- the basic aqueous solution of the alkali metal in (3) above may be an aqueous solution of sodium hydroxide, potassium hydroxide, carbonate or the like.
- examples of the aqueous solution of the carbonate include an aqueous solution using a carbonate-based salt such as an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydrogen carbonate, and an aqueous solution of potassium hydrogen carbonate.
- the crystallization reaction is carried out while controlling the pH in the reaction solution to 10.5 to 11.5. If the pH is less than 10.5, the metal solubility in the reaction solution becomes high, and the metal ratio of the produced precursor decreases, which may deviate from the adjusted composition ratio of the metal salt. On the other hand, if the pH exceeds 11.5, the particle size of the produced precursor becomes too small, the tap density of the positive electrode active material may decrease, and the energy density per volume may decrease.
- the pH in the reaction solution may be 10.7 or more, 10.9 or more, 11.3 or less, or 11.1 or less.
- the crystallization reaction is carried out while controlling the ammonium ion concentration in the reaction solution to 5 to 25 g / L. According to such a configuration, the solubility of nickel and cobalt becomes high, and the particle size can be appropriately adjusted even in a high pH range.
- the tap density of the oxide-based positive electrode active material for an all-solid-state lithium-ion battery produced by using the generated precursor is increased, and the energy density per volume can be increased.
- the ammonium ion concentration in the reaction solution is preferably 10 to 22 g / L, and even more preferably 15 to 20 g / L.
- the crystallization reaction is carried out while controlling the liquid temperature of the reaction liquid to 50 to 65 ° C. If the temperature is less than 50 ° C., the particle size of the produced precursor becomes too large, and when the positive electrode active material is used, the contact area with the solid electrolyte becomes insufficient, so that the resistance becomes large. As a result, the movement of lithium during charging / discharging may be hindered and the rate characteristics may be deteriorated, and if the temperature exceeds 65 ° C., there is a risk that the device may malfunction or the energy cost may be disadvantageous.
- the reaction solution is stirred and reacted in the reaction vessel with the required stirring power per unit volume being 1.8 to 7.3 kW / m 3 .
- the required stirring power per unit volume being 1.8 to 7.3 kW / m 3 .
- a flat disk turbine as shown in FIG. 1 can be used as the shape of the stirring blade.
- the specific gravity of the liquid is 988.07 kg / m 3 , which is the specific gravity of pure water, the blade diameter is 80 mm, and the liquid volume of the reaction liquid is 10 L.
- the required power for stirring per unit volume at each rotation speed can be calculated by the above formula 1.
- a precursor having a small particle size and a high circularity can be produced.
- firing under predetermined conditions as described later it is possible to produce an oxide-based positive electrode active material for an all-solid lithium-ion battery having a small particle size and a high tap density by increasing the circularity.
- an oxide-based positive electrode active material for an all-solid-state lithium-ion battery which has excellent battery characteristics when used in an all-solid-state lithium-ion battery, can be obtained.
- the precursor produced by the above method is sum of the atomic numbers of a metal composed of Ni, Co and Mn (Me). ) And the number of lithium atoms (Li / Me) to be 0.98 to 1.05 to form a lithium mixture, and the lithium mixture in an oxygen atmosphere at 450 to 520 ° C. It includes a step of firing at 680 to 850 ° C. for 2 to 15 hours after firing for 2 to 15 hours.
- the lithium mixture is fired at a temperature lower than 680 ° C, there may be a problem that the precursor and the lithium compound do not sufficiently react, and if the lithium mixture is fired at a temperature higher than 850 ° C, there may be a problem that oxygen is desorbed from the crystal structure.
- an aqueous solution containing a basic aqueous solution of a nickel salt, a cobalt salt, a manganese salt, an ammonia water and an alkali metal is reacted.
- a precursor was prepared by carrying out a crystallization reaction while controlling the pH in the reaction solution to 10.5 to 11.5, the ammonium ion concentration to 5 to 25 g / L, and the liquid temperature to 40 to 65 ° C. Therefore, it is possible to prepare a precursor of a transition metal having high crystallinity and reacting well at the time of firing.
- a positive electrode layer is formed using the oxide-based positive electrode active material for an all-solid-state lithium-ion battery according to the embodiment of the present invention, and an all-solid-state lithium-ion battery including the solid electrolyte layer, the positive electrode layer, and the negative electrode layer is produced. Can be done.
- an oxide-based positive electrode active material precursor and an oxide-based positive electrode active material were prepared in Examples 1 to 13 and Comparative Examples 1 to 6, respectively, and their average particle size D50, circularity, and tap density were obtained.
- the battery characteristics of the all-solid-state lithium-ion battery using the positive electrode active material were measured.
- the contents of Li, Ni, Mn, and Co of the positive electrode active material were measured by an inductively coupled plasma emission spectrophotometer (ICP-OES) and an ion chromatograph method. From the analysis results, we determined the positive electrode active material Li a Ni x Co y Mn a of when expressed in 1-xy metal composition, x, and y. As a result, it was confirmed that the composition was the same as that shown in the positive electrode active material preparation conditions in Table 1 described later.
- the Li / Me ratio in Table 1 corresponds to a in the above formula.
- Examples 1 to 13 and Comparative Examples 1 to 6 Prepare 1.5 moL / L aqueous solutions of nickel sulfate, cobalt sulfate and manganese sulfate, weigh each aqueous solution in a predetermined amount, and prepare a mixed metal salt solution so that Ni: Co: Mn has a mol% ratio in Table 1. After adjustment, the stirring blade was sent to the reaction tank installed inside the container.
- the pH and ammonium ion concentration of the mixed solution in the reaction vessel were adjusted to the values shown in Table 1 with aqueous ammonia and 20.
- a mass% aqueous solution of sodium hydroxide was added to the mixed solution in the reaction vessel, and the composite hydroxide of Ni—Co—Mn was coprecipitated by the crystallization method.
- the temperature of the mixed solution in the reaction vessel was kept warm with a water jacket so as to be the reaction temperature shown in Table 1.
- the specific gravity of the reaction solution is 988.07 kg / m 3
- the blade diameter is 80 mm
- the volume of the reaction solution is 10 L
- the power number Np is 800 rpm in a reaction tank containing 10 L of water.
- Np 3.62 obtained by actually measuring the power of the stirrer, the required power for stirring per unit volume at each rotation speed was calculated by the above formula 1.
- nitrogen gas was introduced into the reaction vessel to prevent oxidation of the coprecipitate generated in the reaction.
- the gas introduced into the reaction vessel is not limited to the above nitrogen gas and can be used as long as it is a gas that does not promote oxidation, such as helium, neon, argon, and carbon dioxide.
- the co-precipitated precipitate was suctioned and filtered, washed with pure water, and dried at 120 ° C. for 12 hours.
- the composition of the prepared Ni-Co-Mn composite hydroxide particles Ni x Co y Mn 1- xy (OH) 2, mean particle diameter D50, was measured circularity.
- the ratio (Li / Me) to the number of lithium (Li) atoms is the value shown in Table 1.
- the mixed powder is filled in an alumina mortar, and fired in a muffle furnace at a firing temperature of 1 shown in Table 1 for 4 hours, and then further.
- An oxide-based positive electrode active material was prepared by firing at the firing temperature 2 shown in Table 1 for 8 hours in an oxygen atmosphere.
- the average particle size D50 of the oxide-based positive electrode active material precursor and the oxide-based positive electrode active material was measured by MT3300EXII manufactured by Microtrac, respectively.
- the tap density of the oxide-based positive electrode active material was determined using a tap densor manufactured by Seishin Enterprise. Specifically, 5 g of the oxide-based positive electrode active material is put into a 10 cc graduated cylinder, installed in the tap denser, vibrated up and down 1500 times, the scale of the graduated cylinder is read, and the volume of the oxide-based positive electrode active material is calculated. Calculated from mass.
- the all-solid-state battery cell was manufactured in a glove box under an argon atmosphere. After coating the oxide-based positive electrode active materials obtained in Examples 1 to 13 and Comparative Examples 1 to 6 with LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 , respectively, 1 at 400 ° C. in an oxygen atmosphere. It was fired for a long time to prepare a positive electrode material active material whose surface was coated with an amorphous layer of lithium niobate. Then mixed with cathode Zaikatsu substance 75mg coated the surface and the sulfide solid electrolyte material Li 3 PS 4 25 mg, to obtain a positive electrode.
- a sulfide-based solid electrolyte material Li 3 PS 4 80 mg using a pellet molding machine and pressed at 5MPa pressure, to form a solid electrolyte layer.
- 10 mg of the positive electrode mixture was put onto the solid electrolyte layer and pressed at a pressure of 30 MPa to prepare a mixture layer.
- the mixture layer of the obtained solid electrolyte layer and the positive electrode active material layer was turned upside down, and a Li foil (5 mm diameter x 0.1 mm thickness) was attached to the SUS plate on the solid electrolyte layer side. It was provided and pressed at a pressure of 20 MPa to form a Li negative electrode layer.
- the laminated body was placed in a battery test cell made of SUS304, and a restraining pressure was applied to obtain an all-solid-state secondary battery, and the initial characteristics (charge capacity, discharge capacity, charge / discharge characteristics) of the 25 ° C. battery were measured.
- the charging / discharging conditions are up to charging condition: CC / CV 4.2V, 0.1C and discharging condition: CC 0.05C, 3.0V.
- Table 1 shows the test conditions and evaluation results according to Examples 1 to 13 and Comparative Examples 1 to 6.
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Abstract
Description
(式中、0.98≦a≦1.05、0.8≦x≦1.0、0≦y≦0.20である。)
で表され、平均粒子径D50が1.0~5.0μmであり、タップ密度が1.6~2.5g/ccであり、円形度が0.85~0.95である全固体リチウムイオン電池用酸化物系正極活物質である。
本発明の実施形態に係る全固体リチウムイオン電池用酸化物系正極活物質は、組成式がLiaNixCoyMn1-x-yO2
(式中、0.98≦a≦1.05、0.8≦x≦1.0、0≦y≦0.20である。)
で表される。
本発明の実施形態に係る全固体リチウムイオン電池用酸化物系正極活物質の前駆体は、組成式が複合水酸化物であるNixCoyMn1-x-y(OH)2(式中、0.8≦x≦1.0、0≦y≦0.20である。)で表される。前駆体の平均粒子径D50は1.0~5.0μmであり、円形度が0.85~0.95である。
式1:単位体積当たりの撹拌所要動力(kW/m3)=動力数Np×液比重(kg/m3)×{回転数(rpm)/60}3×{翼径(m)}5/反応液の液量(m3)
例として、撹拌翼の形状は、図1に示すようなフラットディスクタービンを用いることができる。また、液比重は、純水の比重である988.07kg/m3とし、翼径は80mm、反応液の液量は10Lで計算する。動力数Npは、事前に、水10Lを入れた反応槽にて800rpmの時の攪拌機の動力を実測して求めた「動力数Np=3.62」を用いる。上記の式1にて各回転数での単位体積当たりの撹拌所要動力を算出することができる。
本発明の実施形態に係る全固体リチウムイオン電池用酸化物系正極活物質の製造方法は、上述の方法で製造された前駆体を、Ni、Co及びMnからなる金属の原子数の和(Me)とリチウムの原子数との比(Li/Me)が0.98~1.05となるように混合して、リチウム混合物を形成する工程と、リチウム混合物を酸素雰囲気中、450~520℃で2~15時間焼成した後、さらに680~850℃で2~15時間焼成する工程とを含む。当該リチウム混合物を680℃未満で焼成すると前駆体とリチウム化合物が十分に反応しないという問題が生じるおそれがあり、850℃超で焼成すると結晶構造からの酸素の脱離という問題が生じるおそれがある。
本発明の実施形態に係る全固体リチウムイオン電池用酸化物系正極活物質を用いて正極層を形成し、固体電解質層、当該正極層及び負極層を備えた全固体リチウムイオン電池を作製することができる。
硫酸ニッケル、硫酸コバルトおよび硫酸マンガンの1.5moL/L水溶液をそれぞれ作製し、各水溶液を所定量秤量して、Ni:Co:Mnが表1のmоl%比となるように混合金属塩溶液を調整して、撹拌翼を容器内部に設置した反応槽へ送液した。
式1:単位体積当たりの撹拌所要動力(kW/)=動力数Np×液比重(kg/m3)×{回転数(rpm)/60}3×{翼径(m)}5/反応液の液量(m3)
撹拌翼の形状は、図1に示すようなフラットディスクタービンを用いた。また、反応液の液比重は988.07kg/m3、翼径は80mm、反応液の液量は10Lで計算し、動力数Npは、水10Lを入れた反応槽にて800rpmの時の、攪拌機の動力を実測して求めたNp=3.62を用いて、上記の式1にて各回転数での単位体積当たりの撹拌所要動力を算出した。
酸化物系正極活物質前駆体及び酸化物系正極活物質の平均粒子径D50は、それぞれMicrotrac製MT3300EXIIにより測定した。
酸化物系正極活物質前駆体及び酸化物系正極活物質の円形度は、Malvern社製の粒子画像分析装置「Morphologi G3」にて、取得した2万個以上の粒子の光学画像から、「solidity=0.93」のパラメータを用いてフィルタ処理を行い、測定した。
酸化物系正極活物質のタップ密度は、セイシン企業製のタップデンサーを用いて求めた。具体的には、10ccのメスシリンダーに酸化物系正極活物質5gを投入し、当該タップデンサーに設置し、1500回上下振動し、メスシリンダーの目盛を読み取り、酸化物系正極活物質の体積と質量から算出した。
以下、全固体電池セルの作製はアルゴン雰囲気下のグローブボックス内にて行った。実施例1~13及び比較例1~6で得られた酸化物系正極活物質をそれぞれLiOC2H5とNb(OC2H5)5にて被覆した後に、酸素雰囲気にて400℃で1時間焼成し、ニオブ酸リチウムのアモルファス層にて表面を被覆した正極材活物質を作製した。
次に、当該表面を被覆した正極材活物質75mgと硫化物固体電解質材料Li3PS425mgとを混合し、正極合材を得た。
また、硫化物固体電解質材料Li3PS480mgを、ペレット成形機を用いて5MPaの圧力でプレスし、固体電解質層を形成した。当該固体電解質層の上に正極合材10mgを投入し、30MPaの圧力でプレスして合材層を作製した。
次に、得られた固体電解質層と正極活物質層との合材層の上下を裏返し、固体電解質層側に、SUS板にLi箔(5mm径×厚み0.1mm)を貼り合わせたものを設け、20MPaの圧力でプレスしてLi負極層とした。これによって、正極活物質層、固体電解質層及びLi負極層がこの順で積層された積層体を作製した。
次に、当該積層体をSUS304製の電池試験セルに入れて拘束圧をかけて全固体二次電池とし、25℃電池初期特性(充電容量、放電容量、充放電特性)を測定した。なお、充放電条件は、充電条件:CC/CV 4.2V,0.1C、放電条件:CC 0.05C,3.0Vまでである。
Claims (5)
- 組成式がLiaNixCoyMn1-x-yO2
(式中、0.98≦a≦1.05、0.8≦x≦1.0、0≦y≦0.20である。)
で表され、平均粒子径D50が1.0~5.0μmであり、タップ密度が1.6~2.5g/ccであり、円形度が0.85~0.95である全固体リチウムイオン電池用酸化物系正極活物質。 - ニッケル塩、コバルト塩、マンガン塩、アンモニア水及びアルカリ金属の塩基性水溶液を含有する水溶液を反応液とし、前記反応液中のpHを10.5~11.5、アンモニウムイオン濃度を5~25g/L、液温を50~65℃に制御しながら晶析反応を行う工程を含む、
組成式が複合水酸化物であるNixCoyMn1-x-y(OH)2
(式中、0.8≦x≦1.0、0≦y≦0.20である。)
で表され、平均粒子径D50が1.0~5.0μmであり、円形度が0.85~0.95である全固体リチウムイオン電池用酸化物系正極活物質の前駆体の製造方法。 - 前記晶析反応において、前記反応液を、反応槽内で単位体積当たりの撹拌所要動力を1.8~7.3kW/m3として撹拌して反応させる請求項2に記載の全固体リチウムイオン電池用酸化物系正極活物質の前駆体の製造方法。
- 請求項2~3のいずれか一項に記載の全固体リチウムイオン電池用酸化物系正極活物質の前駆体の製造方法により製造された前駆体を、Ni、Co及びMnからなる金属の原子数の和(Me)とリチウムの原子数との比(Li/Me)が0.98~1.05となるように混合して、リチウム混合物を形成する工程と、
前記リチウム混合物を酸素雰囲気中、450~520℃で2~15時間焼成した後、さらに680~850℃で2~15時間で焼成する工程と、
を含む全固体リチウムイオン電池用酸化物系正極活物質の製造方法。 - 正極層、負極層及び固体電解質層を備え、
請求項1に記載の全固体リチウムイオン電池用酸化物系正極活物質を前記正極層に備えた全固体リチウムイオン電池。
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