Provided is a method of manufacturing high-purity, high-quality manganese sulfate which can be immediately used for manufacturing a lithium ion secondary battery from manganese sulfate waste liquid of a wasted battery. Since impurities are removed from the manganese sulfate waste liquid by using sulfides causing no secondary contamination in the manganese sulfate waste liquid and the manganese sulfate is manufactured by performing evaporation concentration through heating, the manufacturing method is very environment-friendly and economical. Since the manganese recovering process improving the manufacturing yield of the manganese sulfate and the waste water treatment process capable of recycling the source materials and discharging waste water are integrated, the manufacturing method is very efficient and environment-friendly. The manufacturing method is applied to the recycling industry, and thus, it is possible to obtain effects of preventing environmental pollution and facilitating recycling the resources.

A process and method for producing a crystallized metal sulfate. The crystallized metal sulfate may be battery-grade. The method may comprise receiving a metal ion-containing stream and crystalizing a metal sulfate from the stream. The process may comprise receiving a stream from a metal processing plant, and crystalizing a metal sulfate from the stream. The process may be a metal electrowinning process comprising crystalizing a metal ion-containing stream to form a crystallized metal sulfate in a mother liquor. The process or method may comprise returning the mother liquor upstream or to the metal electrowinning process.

A process and method for producing a crystallized metal sulfate. The crystallized metal sulfate may be battery-grade. The method may comprise receiving a metal ion-containing stream and crystalizing a metal sulfate from the stream. The process may comprise receiving a stream from a metal processing plant, and crystalizing a metal sulfate from the stream. The process may be a metal electrowinning process comprising crystalizing a metal ion-containing stream to form a crystallized metal sulfate in a mother liquor. The process or method may comprise returning the mother liquor upstream or to the metal electrowinning process.

The present disclosure describes a process for purifying a MnSO.sub.4 solution including precipitating impurities from the MnSO.sub.4 solution (i) in the presence of a stochiometric excess of fluoride anions, where said stochiometric excess of fluoride anions is calculated on the basis of the fluoride anions required to react with all Mg.sup.2+ and Ca.sup.2+ cations present in the MnSO.sub.4 solution as impurities to form CaF.sub.2 and MgF.sub.2, and (ii) in the presence of sulphide anions. The precipitation is effected at a pH higher than 4, producing a slurry or suspension comprising a purified MnSO.sub.4 solution as a carrier medium and a suspended precipitate which includes MnS, MnF.sub.2, CaF.sub.2 and MgF.sub.2. The slurry or suspension is separated into the purified MnSO.sub.4 solution and the precipitate, whereafter the precipitate is reacted with a SO.sub.4 salt other than MnSO.sub.4 in a solid-state reaction to produce recovered MnSO.sub.4 from the MnS and MnF.sub.2.

The present disclosure describes a process for purifying a MnSO.sub.4 solution including precipitating impurities from the MnSO.sub.4 solution (i) in the presence of a stochiometric excess of fluoride anions, where said stochiometric excess of fluoride anions is calculated on the basis of the fluoride anions required to react with all Mg.sup.2+ and Ca.sup.2+ cations present in the MnSO.sub.4 solution as impurities to form CaF.sub.2 and MgF.sub.2, and (ii) in the presence of sulphide anions. The precipitation is effected at a pH higher than 4, producing a slurry or suspension comprising a purified MnSO.sub.4 solution as a carrier medium and a suspended precipitate which includes MnS, MnF.sub.2, CaF.sub.2 and MgF.sub.2. The slurry or suspension is separated into the purified MnSO.sub.4 solution and the precipitate, whereafter the precipitate is reacted with a SO.sub.4 salt other than MnSO.sub.4 in a solid-state reaction to produce recovered MnSO.sub.4 from the MnS and MnF.sub.2.

A preparation method for a high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling the addition amount of seed crystals. The method comprises the following steps: 1) feeding a ternary metal solution into a reaction kettle containing a first base liquid for reaction, and when the particle size reaches 1.5 to 3.0 m, stopping the feeding, so as to obtain a seed crystal slurry; 2) simultaneously adding the ternary metal solution, a liquid alkali solution, and an ammonia solution in cocurrent flow into a growth kettle containing a second base solution for reaction, when the particle size reaches 6 to 8 m, adding the seed crystal slurry into the reaction system, and controlling the particle size to be 9.0 to 11.0 m by adjusting the feed rate of the seed crystal, so as to obtain the target object. In the preparation method, by adding seed crystals continuously, the crystal plane parameters of 001 peak in the prepared ternary precursor material is lower than the crystal plane parameters of 101 peak, facilitating the embedding of Li ions, and effectively improving the performance of a battery prepared by using the material.

A preparation method for a high nickel ternary precursor capable of preferential growth of crystal planes by adjusting and controlling the addition amount of seed crystals. The method comprises the following steps: 1) feeding a ternary metal solution into a reaction kettle containing a first base liquid for reaction, and when the particle size reaches 1.5 to 3.0 m, stopping the feeding, so as to obtain a seed crystal slurry; 2) simultaneously adding the ternary metal solution, a liquid alkali solution, and an ammonia solution in cocurrent flow into a growth kettle containing a second base solution for reaction, when the particle size reaches 6 to 8 m, adding the seed crystal slurry into the reaction system, and controlling the particle size to be 9.0 to 11.0 m by adjusting the feed rate of the seed crystal, so as to obtain the target object. In the preparation method, by adding seed crystals continuously, the crystal plane parameters of 001 peak in the prepared ternary precursor material is lower than the crystal plane parameters of 101 peak, facilitating the embedding of Li ions, and effectively improving the performance of a battery prepared by using the material.

The present disclosure discloses a wet process for recovering valuable metals from a lithium battery. In the method, a waste lithium battery powder is subjected to selective leaching under the condition that a hydrogen sulfide gas is introduced through pressurization, such that Mn.sup.2+, Li.sup.+, and Al.sup.3+ metal ions enter a first-stage leaching liquor and nickel, cobalt, copper, and iron exist in a first-stage leaching residue in the form of a sulfide; then a pH of the first-stage leaching liquor is adjusted to remove aluminum and manganese, which achieves extremely thorough metal separation and leads to relatively pure products; a first-stage leaching residue is subjected to leaching in an acid liquor under a negative pressure, such that the sulfides of nickel, cobalt, iron, and copper are dissolved in a second-stage leaching liquor, and a hydrogen sulfide gas produced can be recycled in the first-stage leaching procedure through pressurization.

The present disclosure discloses a wet process for recovering valuable metals from a lithium battery. In the method, a waste lithium battery powder is subjected to selective leaching under the condition that a hydrogen sulfide gas is introduced through pressurization, such that Mn.sup.2+, Li.sup.+, and Al.sup.3+ metal ions enter a first-stage leaching liquor and nickel, cobalt, copper, and iron exist in a first-stage leaching residue in the form of a sulfide; then a pH of the first-stage leaching liquor is adjusted to remove aluminum and manganese, which achieves extremely thorough metal separation and leads to relatively pure products; a first-stage leaching residue is subjected to leaching in an acid liquor under a negative pressure, such that the sulfides of nickel, cobalt, iron, and copper are dissolved in a second-stage leaching liquor, and a hydrogen sulfide gas produced can be recycled in the first-stage leaching procedure through pressurization.

The present invention relates to a process for the purification of Manganese sulfate monohydrate (1). The present invention also specifically relates to a cost-effective process for the preparation of pharmaceutical grade Manganese sulfate monohydrate (1) having purity greater than 99.9998% (w/w).