DE112022002537T5 - MANGANE BASED P2 TYPE POSITIVE SODIUM ION BATTERY ELECTRODE MATERIAL PRODUCTION PROCESS - Google Patents

Abstract

A manufacturing method for a manganese-based P2 type positive sodium ion battery electrode material, comprising: adding manganese dioxide to an oxalic acid solution for reaction to obtain a first reaction solution; adding a sodium hydroxide solution to the first reaction solution for reaction to obtain a second reaction solution; performing an ice bath on the second reaction solution, adding a dopant metal-containing alcohol solution for alcohol precipitation and performing solid-liquid separation to obtain a precipitation product; and mixing the precipitate with a manganese source and grinding and calcining the mixture to obtain the manganese-based P2 type positive sodium ion battery electrode material. According to the process, sodium manganate trioxalate is produced by a complexation reaction of oxalic acid and manganese dioxide and neutralization with sodium hydroxide. When the positive sodium ion battery electrode material is manufactured, a precipitate containing sodium manganate trioxalate is used as a sodium source, and no additional sodium source needs to be supplemented during sintering, so that the problem of Na+in is prevented external sodium source is difficult to fully enter a crystal lattice due to a large ionic radius, the sodium residues on the surface of the material are reduced, and the electrochemical performance of the material is further improved.

Description

TECHNICAL FIELD

The present disclosure belongs to the technical field of sodium-ion batteries, and particularly relates to a manufacturing method of a P2-type manganese-based cathode material for sodium-ion batteries.

BACKGROUND

Lithium-ion batteries have been widely used in fields such as portable electronic devices and electric vehicles and have achieved great success and rapid growth. However, the low resource reserves of lithium lead to increasing costs for lithium-ion batteries, and sodium-ion batteries are expected to replace lithium-ion batteries in large-scale energy storage. Among the many cathode materials for sodium-ion batteries, layered transition metal oxides, especially sodium manganese oxides, have attracted great attention from researchers due to their advantages in, for example, high specific capacity and operating voltage, simple manufacturing, environmental friendliness, non-toxicity and low cost.

Layered sodium manganese oxides are one of the cathode materials for sodium-ion batteries and are mainly divided into two structures: P2 phase and O3 phase. Compared to the O3 phase structure, the P2 phase structure has a higher ionic conductivity and a lower diffusion barrier. Therefore, P2-type manganese-based layered oxide is a promising cathode material for sodium-ion batteries.

P2-Na _0.67 MnO ₂ material has excellent electrochemical properties that the theoretical specific capacity is about 173 mAh/g and the average operating voltage is up to 3.8 V, which has attracted great attention from researchers in related fields has. The P2-Na _0.67 MnO ₂ material has a simple synthesis process. Compared with most P2 phase materials, P2-Na _0.67 MnO ₂ material does not require high temperature quenching after sintering to ensure that the material does not undergo P2-P3 phase transition; Through natural cooling after sintering, a P2 structure can be obtained, which is conducive to wide application of materials. P2-Na _0.67 MnO ₂ material will undergo a P2-O2 transition when charged to 4.2 V or more. Besides, there are many factors, such as ordered structure of Na ⁺ vacancy in P2-type layered oxides, which lead to poor electrochemical stability. Elemental doping is an effective means to reduce the degree of ordering of Na ⁺ vacancies, improve the diffusivity of Na ⁺ , improve the loading capacity of materials, inhibit phase transition, and improve cycling stability.

Doping and modifying the material can improve the lattice structure of the electrode material, improve the thermal stability of the material, and increase the ion diffusion capacity of the material to reduce capacity loss during cycling, thereby improving the overall electrochemical performance of sodium-ion batteries.

However, the currently reported doping and modification techniques generally use a manganese source, a sodium source and a doping element to perform solid-state sintering together, which makes it difficult for the dopant to enter the NaMnO ₂ crystal structure or makes the amount of the dopant entering the structure small . It is difficult to achieve the ideal function to stabilize the crystal structure.

In addition, compared with the sintering of lithium battery precursors, since the radius of Li ⁺ ions is smaller than that of Na ⁺ ions, in the one-step high-temperature solid-state synthesis process, Li ⁺ is more likely to enter the material lattice , while it is difficult for Na ⁺ to fully enter the interior of the lattice due to the larger ionic radius, so a large amount of sodium compounds remains on the surface of the material, which affects the electrochemical performance of the material.

SUMMARY

The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present disclosure provides a manufacturing method of a P2-type manganese-based cathode material for sodium-ion batteries, which can improve the doping effect of dopant metal and the intercalation of sodium ions, thereby improving the stability and electrochemical performance of the improving material.

• S1: Zugeben von Mangandioxid zu einer Oxalsäurelösung und Umsetzen bei einer bestimmten Temperatur, um eine erste Reaktionslösung zu erhalten;
• S2: Zugeben einer Natriumhydroxidlösung zu der ersten Reaktionslösung und Umsetzen, bis ein pH-Wert einer resultierenden Lösung bei 4,8-5,2 stabil ist, um eine zweite Reaktionslösung zu erhalten;
• S3: Unterziehen der zweiten Reaktionslösung zu einem Eisbad, Zugeben einer Alkohollösung, die ein Dotierungsmetall für eine Alkoholfällung enthält, und Durchführen einer Fest-Flüssig-Trennung, um ein Fällungsprodukt zu erhalten; und
• S4: Mischen des Fällungsprodukts mit einer Manganquelle und Unterziehen der resultierenden Mischung einem Mahlen und dann einem Kalzinieren, um das Kathodenmaterial vom P2-Typ auf Manganbasis für Natrium-Ionen-Batterien zu erhalten.

According to one aspect of the present disclosure, there is proposed a manufacturing method of a manganese-based P2-type cathode material for sodium-ion batteries, comprising the steps of:

• S1: Adding manganese dioxide to an oxalic acid solution and reacting at a certain temperature to obtain a first reaction solution;
• S2: Adding a sodium hydroxide solution to the first reaction solution and reacting until a pH of a resulting solution is stable at 4.8-5.2 to obtain a second reaction solution;
• S3: subjecting the second reaction solution to an ice bath, adding an alcohol solution containing a dopant metal for alcohol precipitation, and performing solid-liquid separation to obtain a precipitate; and
• S4: Mixing the precipitate with a manganese source and subjecting the resulting mixture to grinding and then calcination to obtain the P2-type manganese-based cathode material for sodium-ion batteries.

In some embodiments of the present disclosure, in step S1, a concentration of the oxalic acid solution is 2-5 mol/L; is a solid-liquid ratio of an added amount of manganese dioxide to the oxalic acid solution (25-80) g: 1 1.

In some embodiments of the present disclosure, in step S1, the reaction is performed at a temperature of 70-90°C.

In some embodiments of the present disclosure, in step S2, a concentration of the sodium hydroxide solution is 0.5-2.0 mol/L.

In some embodiments of the present disclosure, the dopant metal in step S3 is at least one of copper, nickel, or magnesium.

In some embodiments of the present disclosure, in step S3, the alcohol solution containing dopant metal is an alcohol solution of at least one of copper chloride, nickel chloride, magnesium chloride, and magnesium bromide; optionally an alcohol in the alcohol solution is ethanol.

In some embodiments of the present disclosure, in step S3, a concentration of the dopant metal in the alcohol solution containing the dopant metal is 0.05-0.35 mol/L, and an added amount of the alcohol solution containing the dopant metal is 0. 8-1.2 times a volume of the oxalic acid solution.

In some embodiments of the present disclosure, the method further includes washing the precipitate in step S3 after the solid-liquid separation. Preferably, the solid-liquid separation and washing are both carried out under shaded conditions and absolute ethanol is used for washing.

In some embodiments of the present disclosure, the manganese source in step S4 is at least one of manganese dioxide, manganese oxalate, manganese acetate, or manganese carbonate.

In some embodiments of the present disclosure, in step S4, in a material after mixing, an element molar ratio of sodium to manganese (1-3): 3.

In some embodiments of the present disclosure, in step S4, calcination is performed at a temperature of 800-1000°C.

In some embodiments of the present disclosure, in step S4, calcination is performed for 10 to 24 hours.

1. 1. In der vorliegenden Offenbarung wird Natriumtrioxalatomanganat durch eine Komplexierungsreaktion zwischen Oxalsäure und Mangandioxid und Neutralisation durch Natriumhydroxid hergestellt. Die Reaktionsgleichungen sind wie folgt:
   • 2MnO₂+7H₂C₂O₄=2H₃[Mn(C₂O₄)₃]+2CO₂+4H₂O,
   • H₃[Mn(C₂O₄)₃]+3NaOH=Na₃[Mn(C₂O₄)₃]+3H₂O.Bei der Herstellung des Kathodenmaterials für Natrium-Ionen-Batterien wird das Fällungsprodukt bzw. der Niederschlag, das bzw. der Natriumtrioxalatomanganat enthält, als die Natriumquelle verwendet. Während des Sinterns ist es nicht erforderlich, die Natriumquelle zusätzlich zu ergänzen, dadurch das Problem vermeidend, dass es für Na⁺ in der externen Natriumquelle aufgrund des großen Ionenradius schwierig ist, vollständig in das Innere des Gitters einzutreten, das Restnatrium auf der Oberfläche des Materials reduzierend und die elektrochemische Leistung des Materials weiterhin verbessernd.
2. 2. Gleichzeitig mit der Fällung von Natriumtrioxalatomanganat unter Verwendung der Alkohollösung, die das Dotierungsmetall enthält, werden das erzeugte Oxalat und Natriumtrioxalatomanganat co-gefällt, so dass das Natriumelement und das Dotierungsmetall gemeinsam in den Kristall eintreten.
3. 3. Das Einbringen des Dotierungsmetalls stabilisiert die innere Struktur weiterhin, überwindet die Probleme der ungleichmäßigen Dotierung mit Elementen und des leichten Zusammenfalls des Gitters während des Festphasensinterns im Stand der Technik und verbessert die spezifische Kapazität, die Zyklenleistung und die Belastungsfähigkeit des Kathodenmaterials für Natrium-Ionen-Batterien weiterhin.

According to a preferred embodiment of the present disclosure, the present disclosure has at least the following advantageous effects.

1. 1. In the present disclosure, sodium trioxalatomanganate is prepared by a complexation reaction between oxalic acid and manganese dioxide and neutralization by sodium hydroxide. The reaction equations are as follows:
   • 2MnO ₂ +7H ₂ C ₂ O ₄ =2H ₃ [Mn(C ₂ O ₄ ) ₃ ]+2CO ₂ +4H ₂ O,
   • H ₃ [Mn(C ₂ O ₄ ) ₃ ]+3NaOH=Na ₃ [Mn(C ₂ O ₄ ) ₃ ]+3H ₂ O. When producing the cathode material for sodium-ion batteries, the precipitation product or precipitate , which contains sodium trioxalatomanganate, is used as the sodium source. During sintering, it is not necessary to additionally supplement the sodium source, thereby avoiding the problem that it is difficult for Na ⁺ in the external sodium source to fully enter the interior of the grid due to the large ionic radius, the residual sodium on the surface of the material reducing and further improving the electrochemical performance of the material.
2. 2. Simultaneously with the precipitation of sodium trioxalatomanganate using the alcohol solution containing the dopant metal, the produced oxalate and sodium trioxalatomanganate are co-precipitated, so that the sodium element and the dopant metal enter the crystal together.
3. 3. The introduction of the doping metal further stabilizes the internal structure, overcomes the problems of uneven doping of elements and easy collapse of the lattice during solid-state sintering in the prior art, and improves the specific capacity, cycling performance and loading capacity of the cathode material for sodium ions -Batteries still.

BRIEF DESCRIPTION OF DRAWINGS

• 1 ist eine Rasterelektronenmikroskop (REM)-Aufnahme des Kathodenmaterials vom P2-Typ auf Manganbasis für Natrium-Ionen-Batterien, das in Beispiel 1 der vorliegenden Offenbarung hergestellt wurde.

The present disclosure is explained in more detail below in conjunction with the accompanying drawings and examples, in which:

• 1 is a scanning electron microscope (SEM) photograph of the P2-type manganese-based cathode material for sodium-ion batteries prepared in Example 1 of the present disclosure.

DETAILED DESCRIPTION

The concept of the present disclosure and the technical effects produced thereby are clearly and fully described below in conjunction with the examples in order to fully understand the purpose, features and effects of the present disclosure. Obviously, the examples described are only a portion of the embodiments of the present disclosure, rather than all of the embodiments. Based on the embodiments of the present disclosure, other embodiments that will be readily available to those skilled in the art are all within the scope of the present disclosure.

example 1

• (1) 100 ml Oxalsäurelösung mit einer Konzentration von 2 mol/l wurden hergestellt.
• (2) 2,5 g Mangandioxid wurden zu der Oxalsäurelösung gegeben, und die Reaktionstemperatur wurde auf 70°C geregelt bzw. gesteuert, bis der Feststoff vollständig gelöst war, um eine erste Reaktionslösung zu erhalten.
• (3) Nachdem die Reaktion in Schritt (2) abgeschlossen war, wurden sofort 2,0 mol/l Natriumhydroxidlösung zugegeben, bis der pH-Wert der Lösung 4,8-5,2 war. Nachdem die Reaktion abgeschlossen war, wurde eine zweite Reaktionslösung erhalten, und die zweite Reaktionslösung wurde einem Eisbad unterzogen.
• (4) 120 mL Magnesiumchlorid-Ethanollösung mit einer Konzentration von 0,05 mol/l wurden hergestellt und zu der zweiten Reaktionslösung unter einem Eisbad in Schritt (3) für eine Alkoholfällung zugegeben, wobei das Ethanol absolutes Ethanol war.
• (5) Eine Fest-Flüssig-Trennung wurde im Dunkeln durchgeführt, und das erhaltene Fällungsprodukt wurde mit absolutem Ethanol gewaschen.
• (6) Das gewaschene Fällungsprodukt wurde mit Mangandioxid gemischt und dann gemahlen.

In this example, a P2-type manganese-based cathode material for sodium-ion batteries was prepared. The specific process was as follows:

• (1) 100 ml of oxalic acid solution with a concentration of 2 mol/L was prepared.
• (2) 2.5 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled at 70°C until the solid was completely dissolved to obtain a first reaction solution.
• (3) After the reaction in step (2) was completed, 2.0 mol/L of sodium hydroxide solution was immediately added until the pH of the solution was 4.8-5.2. After the reaction was completed, a second reaction solution was obtained, and the second reaction solution was subjected to an ice bath.
• (4) 120 mL of magnesium chloride ethanol solution with a concentration of 0.05 mol/L was prepared and added to the second reaction solution under an ice bath in step (3) for alcohol precipitation, where the ethanol was absolute ethanol.
• (5) Solid-liquid separation was carried out in the dark, and the resulting precipitate was washed with absolute ethanol.
• (6) The washed precipitate was mixed with manganese dioxide and then ground.

In the material, after mixing, the molar element ratio of sodium to manganese was 1:3. The material was calcined at 800 °C for 24 h to obtain the P2-type manganese-based cathode material for sodium-ion batteries.

Example 2

• (1) 100 ml Oxalsäurelösung mit einer Konzentration von 4 mol/l wurden hergestellt.
• (2) 5,0 g Mangandioxid wurden zu der Oxalsäurelösung zugegeben, und die Reaktionstemperatur wurde auf 80°C geregelt bzw. gesteuert, bis der Feststoff vollständig gelöst war, um eine erste Reaktionslösung zu erhalten.
• (3) Nachdem die Reaktion in Schritt (2) abgeschlossen war, wurden sofort 1,0 mol/l Natiumhydroxidlösung zugegeben, bis der pH-Wert der Lösung 4,8-5,2 war. Nachdem die Reaktion abgeschlossen war, wurde eine zweite Reaktionslösung erhalten, und wurde die zweite Reaktionslösung einem Eisbad unterzogen.
• (4) 100 ml Nickelchlorid-Ethanollösung mit einer Konzentration von 0,07 mol/l wurden hergestellt und in Schritt (3) unter einem Eisbad für eine Alkoholfällung zu der zweiten Reaktionslösung zugegeben, wobei das Ethanol absolutes Ethanol war.
• (5) Eine Fest-Flüssig-Trennung wurde im Dunkeln durchgeführt, und das erhaltene Fällungsprodukt wurde mit absolutem Ethanol gewaschen.
• (6) Das gewaschene Fällungsprodukt wurde mit Manganoxalat gemischt und dann gemahlen. In dem Material war nach dem Mischen das molare Element-Verhältnis von Natrium zu Mangan 2:3. Das Material wurde bei 900 °C für 18 h kalziniert, um das Kathodenmaterial vom P2-Typ auf Manganbasis für Natrium-Ionen-Batterien zu erhalten.

In this example, a P2-type manganese-based cathode material for sodium-ion batteries was prepared. The specific process was as follows:

• (1) 100 ml of oxalic acid solution with a concentration of 4 mol/L was prepared.
• (2) 5.0 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled at 80°C until the solid was completely dissolved to obtain a first reaction solution.
• (3) After the reaction in step (2) was completed, 1.0 mol/L of sodium hydroxide solution was immediately added until the pH of the solution was 4.8-5.2. After the reaction was completed, a second reaction solution was obtained, and the second reaction solution was subjected to an ice bath.
• (4) 100 ml of nickel chloride ethanol solution with a concentration of 0.07 mol/L was prepared and added to the second reaction solution in step (3) under an ice bath for alcohol precipitation, where the ethanol was absolute ethanol.
• (5) Solid-liquid separation was carried out in the dark, and the resulting precipitate was washed with absolute ethanol.
• (6) The washed precipitate was mixed with manganese oxalate and then ground. In the material, after mixing, the molar element ratio of sodium to manganese was 2:3. The material was calcined at 900 °C for 18 h to obtain the P2-type manganese-based cathode material for sodium-ion batteries.

Example 3

• (1) 100 ml Oxalsäurelösung mit einer Konzentration von 5 mol/l wurden hergestellt.
• (2) 8,0 g Mangandioxid wurden zu der Oxalsäurelösung zugegeben, und die Reaktionstemperatur wurde auf 90°C geregelt bzw. gesteuert, bis der Feststoff vollständig gelöst war, um eine erste Reaktionslösung zu erhalten.
• (3) Nachdem die Reaktion in Schritt (2) abgeschlossen war, wurden sofort 2,0 mol/l Natriumhydroxidlösung zugegeben, bis der pH-Wert der Lösung 4,8-5,2 war. Nachdem die Reaktion abgeschlossen war, wurde eine zweite Reaktionslösung erhalten, und wurde die zweite Reaktionslösung einem Eisbad unterzogen.
• (4) 80 ml Kupferchlorid-Ethanollösung mit einer Konzentration von 0,35 mol/l wurden hergestellt und in Schritt (3) für eine Alkoholfällung unter einem Eisbad zu der zweiten Reaktionslösung zugegeben, wobei das Ethanol absolutes Ethanol war.
• (5) Eine Fest-Flüssig-Trennung wurde im Dunkeln durchgeführt, und das erhaltene Fällungsprodukt wurde mit absolutem Ethanol gewaschen.
• (6) Das gewaschene Fällungsprodukt wurde mit Mangancarbonat gemischt und dann gemahlen. In dem Material nach dem Mischen war das molare Element-Verhältnis von Natrium zu Mangan 1:1. Das Material wurde bei 1000 °C für 10 h kalziniert, um das Kathodenmaterial vom P2-Typ auf Manganbasis für Natrium-Ionen-Batterien zu erhalten.

In this example, a P2-type manganese-based cathode material for sodium-ion batteries was prepared. The specific process was as follows:

• (1) 100 ml of oxalic acid solution with a concentration of 5 mol/L was prepared.
• (2) 8.0 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled at 90°C until the solid was completely dissolved to obtain a first reaction solution.
• (3) After the reaction in step (2) was completed, 2.0 mol/L of sodium hydroxide solution was immediately added until the pH of the solution was 4.8-5.2. After the reaction was completed, a second reaction solution was obtained, and the second reaction solution was subjected to an ice bath.
• (4) 80 ml of copper chloride ethanol solution with a concentration of 0.35 mol/L was prepared and added to the second reaction solution in step (3) for alcohol precipitation under an ice bath, where the ethanol was absolute ethanol.
• (5) Solid-liquid separation was carried out in the dark, and the resulting precipitate was washed with absolute ethanol.
• (6) The washed precipitate was mixed with manganese carbonate and then ground. In the material after mixing, the molar element ratio of sodium to manganese was 1:1. The Mate rial was calcined at 1000 °C for 10 h to obtain the P2-type manganese-based cathode material for sodium-ion batteries.

Comparative example 1

• Manganoxalat und Natriumoxalat wurden gemäß einem molaren Element-Verhältnis von Natrium zu Mangan von 2:3 gemischt, dann gemahlen und bei 900°C für 18 h kalziniert, um ein Kathodenmaterial auf Manganbasis für Natrium-Ionen-Batterien zu erhalten.

In this comparative example, a P2-type manganese-based cathode material for sodium-ion batteries was prepared. This comparative example differed from Example 2 in that in Comparative Example 1 a sodium source and a manganese source were sintered directly in the solid phase without doping. The specific process was as follows:

• Manganese oxalate and sodium oxalate were mixed according to a molar element ratio of sodium to manganese of 2:3, then milled and calcined at 900 °C for 18 h to obtain a manganese-based cathode material for sodium-ion batteries.

Test example

The cathode material for sodium ion batteries prepared in Examples 1-3 and Comparative Example 1 was assembled into sodium ion half cells, respectively. In a voltage range of 2.0 to 3.8 V at a rate of 0.8 °C, the capacity per gram at the first charge and discharge and the capacity per gram after 100 charge and discharge cycles were tested, and the results are shown in Table 1 shown. Table 1 Electrochemical properties of cathode materials for sodium-ion batteries Capacity per gram on first charge and discharge at a rate of 0.8°C mAh/g Capacity per gram after 100 times charging and discharging mAh/g example 1 147.4 134.8 Example 2 158.3 145.1 Example 3 159.6 146.7 Comparative example 1 128.4 86.7

From Table 1, it can be seen that the capacity per gram at first charge and discharge and the cycling performance of the cathode material for sodium-ion batteries obtained by direct solid-state sintering in Comparative Example 1 were significantly lower than those of the Examples. This is because in the examples, the precipitate containing sodium trioxalatomanganate is used as the sodium source, and the co-precipitation of sodium trioxalatomanganate and the metal-doped oxalate allows the sodium element and the dopant metal to enter the crystal together, which avoiding uneven element doping and lattice collapse during sintering, improving the specific capacity and cycling performance of the cathode material for sodium-ion batteries.

The examples of the present disclosure have been described in detail above in connection with the drawings. However, the present disclosure is not limited to the above-mentioned examples, and various modifications can be made without departing from the purpose of the present disclosure within the knowledge possessed by those skilled in the art. Furthermore, in the case where there is no conflict, the examples of the present disclosure and the features in the examples may be combined with each other.

Claims (10)

A manufacturing process for a P2-type manganese-based cathode material for sodium-ion batteries, comprising the steps of: S1: adding manganese dioxide to an oxalic acid solution and reacting at a certain temperature to obtain a first reaction solution; S2: Adding a sodium hydroxide solution to the first reaction solution and reacting until a pH of a resulting solution is stable at 4.8-5.2 to obtain a second reaction solution; S3: subjecting the second reaction solution to an ice bath, adding an alcohol solution containing a dopant metal for alcohol precipitation, and performing solid-liquid separation to achieve precipitation to obtain the product; and S4: mixing the precipitate with a manganese source and subjecting a resulting mixture to grinding and then calcination to obtain the P2-type manganese-based cathode material for sodium-ion batteries. Manufacturing process according to Claim 1 , where in step S1 a concentration of the oxalic acid solution is 2-5 mol/l. Manufacturing process according to Claim 1 , wherein in step S1 the reaction is carried out at a temperature of 70-90 ° C. Manufacturing process according to Claim 1 , where in step S2 a concentration of the sodium hydroxide solution is 0.5-2.0 mol/l. Manufacturing process according to Claim 1 , wherein in step S3 the doping metal is at least one of copper, nickel or magnesium. Manufacturing process according to Claim 1 or 5 , wherein in step S3, the alcohol solution containing dopant metal is an alcohol solution of at least one of copper chloride, nickel chloride, magnesium chloride or magnesium bromide; optionally an alcohol in the alcohol solution is ethanol. Manufacturing process according to Claim 1 , wherein in step S3, a concentration of the dopant metal in the alcohol solution containing dopant metal is 0.05-0.35 mol/l and an added amount of the alcohol solution containing dopant metal is 0.8-1.2 times a volume the oxalic acid solution. Manufacturing process according to Claim 1 , wherein in step S4 the manganese source is at least one of manganese dioxide, manganese oxalate, manganese acetate or manganese carbonate. Manufacturing process according to Claim 1 , where in step S4 in a material after mixing a molar element ratio of sodium to manganese (1-3): 3. Manufacturing process according to Claim 1 , wherein in step S4 the calcination is carried out at a temperature of 800-1000 ° C.