CN109897964A

CN109897964A - Manganese-containing material recovery and regeneration method

Info

Publication number: CN109897964A
Application number: CN201910220866.6A
Authority: CN
Inventors: 郑卓群; 许佳宁
Original assignee: Ningbo Xingshu New Energy Technology Co ltd
Current assignee: Ningbo Xingshu New Energy Technology Co ltd
Priority date: 2019-03-22
Filing date: 2019-03-22
Publication date: 2019-06-18

Abstract

The invention discloses a method for recovering and regenerating manganese-containing materials, which can reduce high-valence insoluble metal ions in the manganese-containing materials into low-valence soluble ions so as to achieve the purpose of efficiently leaching metal elements; the method has short process route and low cost, can be realized by one-step reaction, and has high recovery rate; the invention is based on the closed-loop circulation of metal elements, and the material recovered and regenerated by the technology of the invention has no difference from the newly prepared material in performance or appearance. The method has wide application range, can recycle the anode materials of the retired lithium ion secondary battery, including the anode materials of a layered structure, a spinel structure, polyanions and the like, can recycle the anode materials of the waste zinc-manganese battery, the waste alkali-manganese battery and the waste lithium-manganese primary battery, and can recycle the invalid manganese catalyst and the manganese adsorbent.

Description

Manganese-containing material recovery and regeneration method

Technical Field

The invention relates to the field of comprehensive utilization of waste resources, in particular to a method for recovering and regenerating manganese-containing materials in the field of batteries.

Background

The manganese-containing material is mainly derived from batteries using manganese-based materials, including zinc-manganese dry batteries, alkaline-manganese batteries, lithium-manganese primary batteries, lithium-ion secondary batteries of which the positive electrode material contains manganese elements, manganese catalysts, manganese adsorbents and the like. Particularly, with the vigorous development of the new energy automobile industry, the usage amount of the lithium ion secondary battery is rapidly increased, and the amount of manganese-containing materials is increased year by year. Meanwhile, in the aftermarket, the new energy automobile power battery has already entered the retirement period, and recycling and echelon utilization become a key point of enterprise competition. The method has the advantages that the development of resources such as lithium, cobalt, nickel and manganese and the construction of a power battery recycling system are integrated, a closed loop is formed from battery disassembly to material recycling, a good development environment of the power battery industry is created, and the healthy and sustainable development of the industry is promoted, so that the method is significant.

The disassembly and recovery of the lithium ion power battery comprises the pretreatment processes of discharge, disassembly, sorting, pyrolysis degumming and the like of the retired battery, and valuable metal materials are obtained through a specific recovery process. The existing recovery process comprises a dry method, a wet method, a bioleaching method and the like, and the wet method is mostly researched and applied at present. For example, chinese patent (CN 102665912 a) recovers cobalt and manganese from a waste battery ternary positive electrode material by an extraction method, and prepares cobalt and manganese extracts into a Co-Mn-Br liquid catalyst (CMB catalyst for short). The extraction method relates to solvent extraction and solvent elution, and has the disadvantages of complicated process and large demand for organic solvent and water. How to realize the purification treatment and the recycling of water is a big problem. Chinese patent No. (CN 102956935A) separates and recovers the metal elements (Li, ni, co, mn) in the ternary material of the waste power battery by a precipitation method. Although the method realizes the recovery of all metal elements in the ternary material, the method relates to multi-step chemical reaction and various chemical reagents, the pH value of the solution needs to be repeatedly and accurately controlled, and the recovered inorganic salts of the metal elements cannot be directly used for preparing the ternary material, wherein the recovered lithium salt, cobalt salt, nickel salt and manganese salt are lithium phosphate, cobalt sulfide, nickel oxalate and manganese carbonate respectively.

The recycling of metal resources in waste alkaline batteries is also of great significance. It is known that 96% of alkaline batteries produced in China are zinc-manganese batteries and alkaline-manganese batteries, and the main components of the alkaline batteries are heavy metals such as manganese, zinc and the like. The heavy metal components of the waste batteries can overflow along with seepage liquid no matter the waste batteries are buried in the atmosphere or underground, so that the pollution of underground water and soil is caused, and the health of human beings is seriously harmed after long-term accumulation. The data show that 3000 tons of waste alkaline batteries can recover 141 tons of miscellaneous zinc ingots, 300 tons of metallurgical manganese dioxide, 260 tons of iron sheet, 181 tons of electrolytic zinc and 340 tons of electrolytic manganese dioxide, the value is equivalent to the cost for developing two medium-sized mines in China, and even more, the materials are non-renewable disposable resources. Along with the popularization of garbage classification and collection, the centralized treatment of waste batteries is imperative, and the recycling technology is exactly the time for realizing social and economic benefits. Chinese patent No. (CN 102569838A) discloses a method for comprehensively utilizing metal resources such as manganese, iron and zinc in waste zinc-manganese dry batteries, waste alkali-manganese batteries, waste lithium-manganese primary batteries and the like through pyrometallurgy. Although the method has the advantages of resource utilization, high recovery rate and the like, the method has the problems of high energy consumption, waste gas emission and the like. Chinese patent (CN 104229898A) discloses a method for preparing high-purity manganese sulfate and zinc sulfate by using waste zinc-manganese batteries as raw materials through the working procedures of sulfuric acid dissolution, iron powder replacement, oxidation neutralization deferrization, extraction, purification, separation and the like. The method has many steps and uses an extraction process, which is not ideal.

Disclosure of Invention

The invention provides a method for recycling manganese-containing materials to solve the technical problem. The manganese-containing material is mainly derived from batteries using manganese-based materials, including zinc-manganese dry batteries, alkaline-manganese batteries, lithium-manganese primary batteries, lithium-ion secondary batteries of which the positive electrode material contains manganese elements, manganese catalysts, manganese adsorbents and the like.

One of the purposes of the invention is to provide a method for recycling manganese-containing materials, which utilizes a liquid-phase oxidation-reduction reaction leaching separation mode to realize the recycling of manganese materials, and has the technical effects of simple and easily controlled process, no pollution, high efficiency and energy conservation.

The invention also aims to provide a method for recycling the manganese-containing material, which can realize the manufacturing and production of the target electrode material on the basis of the manganese-containing material, simplify the process and improve the resource utilization rate.

In order to achieve the above object, according to a first aspect of the embodiments of the present invention, the technical solution adopted by the present invention is:

the manganese element recovery method for the manganese-containing material comprises the following steps:

the method comprises the steps of reacting a manganese-containing material with an acidic solution containing a reducing agent, and carrying out solid-liquid separation on a reactant after the reaction to obtain a leaching solution and filter residues for leaching manganese metal elements in the manganese-containing material, wherein the manganese-containing material contains the manganese elements, and the chemical valence of the manganese is at least one valence state of +3 valence state, +4 valence state or +6 valence state.

Preferably, the method further comprises the following steps after the leaching solution and the filter residue are obtained: washing the filter residue for a plurality of times to obtain washing liquid and washing filter residue, mixing the washing liquid with the leaching liquid, reacting the washing filter residue with an acid solution containing aldehyde compounds, stirring and heating, carrying out solid-liquid separation after reaction to obtain a secondary leaching liquid and secondary reaction filter residue, and leaching metal elements in the washing filter residue.

Preferably, the reducing agent comprises an aldehyde compound; wherein the molecular structural formula of the aldehyde compound is as follows:

wherein R is at least one selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or R is selected from a group containing at least one element of boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine and iodine.

Preferably, R in the molecular structural formula of the aldehyde compound is hydrogen or an alkyl group having 1 to 5 carbon atoms.

As a further preference, the aldehyde compound is one or more of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-valeraldehyde, 2-methylpropionaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde.

Preferably, the solid-to-liquid ratio of the manganese-containing material to the acidic solution containing the aldehyde compound is 10 to 2000g/L, the reaction temperature is 20 to 100 ℃, and the reaction time is 0.1 to 36 hours.

According to another preferred embodiment of the present invention, the reducing agent further comprises one or more of sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, sodium thiosulfate, hydrogen peroxide, glucose, sucrose, cellulose, corn stalks.

Preferably, the acidic solution is an inorganic acid and/or an organic acid, the inorganic acid is any one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the organic acid is any one or more of oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid.

According to a second aspect of the embodiments of the present invention, the present invention provides a method for regenerating a manganese-containing material, wherein the manganese-containing material is a positive electrode material of a retired power lithium ion secondary battery, and inert gas or nitrogen is introduced during a reaction process for protection, comprising the following steps:

(1) Recovery of manganese-containing materials: according to the method for recovering the manganese-containing material, leaching solution and filter residue are obtained;

(2) Preparing a precursor solution: adjusting the content of each metal element in the leachate according to the element composition and content in the leachate to ensure that the molar ratio of each metal element is consistent with the chemical formula of the target cathode material, thereby obtaining a precursor solution;

(3) Preparing a target positive electrode material precursor: preparing a target anode material precursor by using a precursor solution for a coprecipitation method preparation process, and simultaneously obtaining a lithium ion-containing solution;

(4) Recovering lithium element in the liquid phase to obtain a lithium source compound;

(5) Preparing a target cathode material: and (4) preparing the target cathode material by using the target cathode material precursor in the step (3) and the lithium source compound recovered in the step (4) through a cathode material firing process.

Preferably, in the step (2), the target cathode material has a chemical formula of Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O ₂ 、Li _1+η [Mn _2-a Mˊ _a ]O ₄ Or xLi ₂ MnO ₃ ·(1-x)LiNO ₂ Adding one or more of water-soluble salts of nickel, cobalt and manganese and M, M 'or N to the leachate to adjust the content of each metal element In the leachate according to the chemical formula of the target cathode material, wherein the doping element M, M' or N is any one or more of metal elements Ni, co, mn, na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V, cr, fe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd and Sm.

Preferably, the anion of the water-soluble salt is at least one of a chloride ion, a sulfate ion, a nitrate ion, an oxalate ion, a hydrogen phosphate ion, a dihydrogen phosphate ion, and an acetate ion.

Further preferably, the anion of the water-soluble salt corresponds to the anion of the acid in the leachate.

Preferably, the coprecipitation method comprises the following steps: and adding an ammonia water solution and/or an alkaline water solution into the precursor solution, carrying out coprecipitation reaction on metal ions except lithium, and carrying out solid-liquid separation to obtain a target anode material precursor and a lithium ion-containing solution respectively.

Preferably, the aqueous ammonia solution is an aqueous solution containing at least one of ammonia, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate and ammonium sulfate, and has a concentration of 0.1 to 1 mol/L.

Preferably, the aqueous alkali solution is an aqueous solution containing at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, and has a concentration of 0.5 to 5 mol/L.

Preferably, the pH of the mixed solution is 9 to 12.5, the reaction temperature is 30 to 80 ℃, the reaction stirring speed is 100 to 2000rpm, and the reaction time is 1 to 24 hours.

Preferably, the pH value of the mixed solution in the nucleation stage at the early stage of the reaction is higher than that in the particle growth stage at the later stage.

Preferably, the method for preparing the target cathode material precursor in step (3) includes a step of doping or coating modifying the precursor.

Preferably, the method for recovering lithium element in the liquid phase in step (4) includes introducing carbon dioxide or adding one or more of carbonate, phosphate and fluoride into the lithium ion-containing solution, or separating and extracting lithium by a membrane method.

Preferably, the lithium source compound obtained in the step (4) is at least one of a hydroxide of lithium, an oxide of lithium, a sulfide of lithium, a carbonate of lithium, a nitrate of lithium, an acetate of lithium, and a halide of lithium.

Preferably, the step (5) is followed by the steps of: and carrying out doping and/or coating modification on the target positive electrode material.

According to a third aspect of embodiments of the present invention, there is provided a method for regenerating a manganese-containing material, which is a positive electrode material of an alkaline manganese battery, including the steps of:

(1) Recovery of manganese-containing materials: according to the method for recovering the manganese-containing material, leaching liquid and filter residue are obtained;

(2) Preparing electrolytic manganese dioxide electrolyte: adjusting the content of each component in the leachate according to the composition and content of elements in the leachate to ensure that the composition of the leachate is consistent with the electrolytic liquid phase of electrolytic manganese dioxide, so as to obtain an electrolyte solution;

(3) Electrolysis: heating the electrolyte solution to 80-98 ℃, conveying the electrolyte solution to an electrolytic cell, wherein the anode of the electrolytic cell is a titanium-based manganese alloy plate or strip, and electrolyzing to obtain a mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product;

(4) Rinsing: crushing the mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product into manganese dioxide powder with the particle size of 20-40 mm, then putting the manganese dioxide powder into a rinsing tank for rinsing, and sequentially carrying out four-stage rinsing processes of water washing, alkali washing, backwashing and water washing;

(5) Grinding: after the rinsing is qualified, grinding the materials according to the required granularity;

(6) Mixing to obtain the electrolytic manganese dioxide product which can be used for alkaline manganese batteries.

More preferably, the temperature of the electrolyte in step (3) is 90 to 95 ℃.

Preferably, in the step (3), the electrolysis conditions are as follows: the electrolysis temperature is 95-98 ℃, the anode current density is 60-70A/m 2, the electrolyte sulfuric acid concentration is 30-50 g/L, and the electrolysis period is 10-12 days.

Preferably, in the step (4), the temperature of water washing and back washing is 90-95 ℃, the temperature of alkali washing is 55-70 ℃, and the rinsing cycle is 29-34 h.

Preferably, in the step (6), the blending time is 16 to 24 hours.

The method is also suitable for regenerating manganese-containing materials obtained from waste zinc-manganese dry batteries, waste lithium-manganese primary batteries, spent manganese catalysts, spent manganese adsorbents and the like.

Compared with the prior art, the reduction leaching method adopted by the invention can reduce the high-valence insoluble metal ions in the manganese-containing material into low-valence soluble ions, and the by-product after the reaction is gas or low-boiling micromolecular organic matter which is easy to remove from the system; the leaching recovery process route is short and low in cost, the metal ions in the anode material can be leached through one-step reaction, the leaching rate is high, and the leaching time is short; based on the closed-loop circulation of metal elements, the main metal elements in the manganese-containing material can be recycled and regenerated by the technology, the application range is wide, the anode material of the retired lithium ion secondary battery can be recycled and regenerated, the anode material comprises the anode materials of a layered structure, a spinel structure, polyanions and the like, the anode materials of a waste zinc-manganese battery, a waste alkali-manganese battery and a waste lithium-manganese primary battery can be recycled, and the invalid manganese catalyst and a manganese adsorbent can be recycled.

Drawings

FIG. 1 is a schematic flow diagram of a method for recovering manganese-containing materials in accordance with the present invention.

FIG. 2 is a schematic flow diagram of a first process for regenerating manganese-containing materials (from the cathode material of a lithium ion battery) in accordance with the present invention.

Fig. 3 is a schematic flow diagram of a second process for regenerating a manganese-containing material (from the positive electrode material of an alkaline manganese cell) in accordance with the present invention.

Detailed Description

The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.

In the first aspect of the embodiment of the invention, a method for recovering a manganese-containing material is provided, the manganese-containing material contains manganese, the chemical valence of manganese is at least one valence state of +3 valence, +4 valence or +6 valence, the manganese-containing material is reacted with an acidic solution containing aldehyde compounds, and solid-liquid separation is performed after the reaction to obtain leachate and filter residue, so that leaching of manganese metal elements in waste materials is realized; the method comprises the following specific steps:

(a) Reacting a manganese-containing material with an acidic solution containing an aldehyde compound, and heating if the reaction temperature is too low;

(b) Carrying out solid-liquid separation to obtain a leaching solution and filter residues, and leaching metal elements in the manganese-containing waste; the aldehyde compound includes at least one compound having the following molecular structural formula:

r is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or R is selected from a group containing at least one element of boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine and iodine.

The invention provides an aldehyde compound and a leaching process, under the action of an acid environment and the aldehyde compound, manganese elements in manganese-containing materials are efficiently leached, and the leaching rate can reach more than 98%.

In the aldehyde compound of the present invention, it is preferable that R is hydrogen or an alkyl group having 1 to 5 carbon atoms in the molecular structural formula of the compound. The compound with the structure is easy to purchase in the market and low in cost, and meets the requirement of industrial production; in addition, the oxidized product of the compound with the structure is small in molecule and simple in structure, for example, a gas molecule can be removed as a by-product through a gas-liquid separation method, and a compound with a low boiling point can be removed from a system through a distillation method or a reduced pressure distillation method. Further preferably, the aldehyde compound is any one or more of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-valeraldehyde, 2-methylpropionaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde, and the like.

The corresponding chemical formula is as follows:

。

in addition to the aldehyde compound, the acidic solution may contain one or more other compounds having reducing properties, such as sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, sodium thiosulfate, hydrogen peroxide, glucose, sucrose, cellulose, cornstalks, and the like.

The anode material of the retired power lithium ion secondary battery is a main source of manganese-containing materials, and besides the retired lithium ion battery anode material, the method provided by the invention can also be used for recovering anode material waste materials generated in the production of the manganese-containing anode material or the manufacturing process of the lithium ion battery, wherein the manganese-containing raw material source comprises the following components:

the manganese-containing material is from a lithium-manganese primary battery, in the primary battery, metal lithium is used as an anode, manganese dioxide is used as a cathode, and the chemical valence of a manganese element is + 4.

The manganese-containing material is derived from a manganese catalyst, typically a high activity manganese dioxide (MnO) as the major component ₂ ) Wherein the chemical valence of the manganese element is +4 valence.

The manganese-containing material is from a manganese adsorbent. For example, a manganese adsorbent for removing formaldehyde, whose major active ingredient is manganese dioxide (MnO) of high specific surface area ₂ ) Wherein the chemical valence of the manganese element is +4, and the aim of removing formaldehyde is achieved by absorbing formaldehyde and catalyzing and oxidizing the formaldehyde. For example, an inorganic manganese sorbent material, also known as an ion sieve, has a spinel structure with a precursor of the chemical formula LiMn ₂ O ₄ Acid leaching to remove lithium to obtain p-Li ⁺ Spinel type ion sieves with specific selective adsorption.

At present, the anode material for power batteries is mainly lithium transition metal oxide, including LiCoO with a layered structure ₂ 、Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O ₂ 、Li _1+δ [Ni _1-x-y Co _x Al _y ]O ₂ LiMn of spinel structure ₂ O ₄ Polyanionic positive electrode materials such as olivine-structured LiFePO ₄ Lithium-rich manganese-based positive electrode materials such as xLi, which are currently still in research and development stage ₂ MnO ₃ .(1-x)LiMO ₂ (M = Ni, co, mn, etc., and 5V positive electrode materials such as LiNi _0.5 Mn _1.5 O ₄ And the like.

In addition, the surface coating modification of the positive electrode material is one of the important means for improving the electrochemical performance of the material. Common coating materials are ZnO and ZrO ₂ 、AlPO ₄ 、Li ₃ PO ₄ 、Al ₂ O ₃ 、AlF ₃ 、SiO ₂ 、TiO ₂ MgO and Li, a boron-lithium compound ₂ O-2B ₂ O ₃ And the like, and organic polymer materials such as polyaniline.

Besides different elemental compositions and crystal structures, the positive electrode material can have various geometric structures: such as a core-shell structure, the spherical core portion of the positive electrode material powder particles is composed of a high-capacity, high-nickel positive electrode material, such as LiNi _0.8 Co _0.2 O ₂ Or LiNi _0.8 Co _0.1 Mn _0.1 O ₂ The spherical shell portion of the powder particles is composed of a positive electrode material having good thermal stability and long cycle life, such as LiNi _0.5 Mn _0.5 O ₂ (ii) a Also U.S. patents (application No. US13/978067 and application No. US13/978041, etc.) discloseThe high-capacity concentration gradient cathode material is provided.

The retired lithium ion battery positive electrode material comprises all the types of positive electrode materials mentioned above, wherein the materials contain manganese, and the chemical valence of the manganese is +4 or + 3. The anode materials of the retired lithium ion battery can be roughly classified into the following three types.

The first kind of retired lithium ion battery positive electrode material has a general formula of Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O _2-β P _β Wherein, the doping element M is at least one of metal elements Na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V, cr, fe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd and Sm, the doping element P is F or S, delta is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to 0.5,0 and less than or equal to 1,0 and less than or equal to 1,0 and less than or equal to z 0.2, and 0 zxft 6253 and less than or equal to 0.5,0 and less than or equal to 3238 and less than or equal to Y and less than or equal to 1,0 and less than or equal to z 0.2<x+y+z≤1。

When β =0, the formula is represented by Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O ₂ . In this case, common materials are: liNi _0.5 Co _0.2 Mn _0.3 O ₂ 、LiNi _0.6 Co _0.2 Mn _0.2 O2、LiNi _0.5 Co _0.25 Mn _0.25 O ₂ 、LiNi _0.5 Co _0.2 Mn _0.3 O ₂ 、LiNi _0.815 Co _0.15 Al _0.035 O ₂ And the like.

When beta is more than 0 and less than or equal to 0.5, the non-metallic elements such as F or S are doped with oxygen sites, so that the thermal stability and the cycling stability of the material can be improved. In general, it is preferable to control the doping amount of F or S to be within 5 mol% of the amount of the oxygen element. If the doping amount is too small, the improvement of the properties of the material is not significant, and if the doping amount is too large, the electron conductivity of the material may be reduced, and the capacity exertion of the material may be suppressed.

The second kind of retired lithium ion battery positive electrode material has a general formula of Li _1+η [Mn _2-a Mˊ _a ]O _4-m P _m Wherein, the doping element M' is metal elements Ni, co, na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V and CrFe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd and Sm, the doping element P is F or S, eta is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to a and less than or equal to 2,0 and less than or equal to m and less than or equal to 0.5.

When m =0, the formula is represented by Li _1+η [Mn _2-a Mˊ _a ]O ₄ . When m is more than 0 and less than or equal to 0.5, the non-metal elements such as F or S are doped with oxygen sites, so that the thermal stability and the cycling stability of the material can be improved.

The third kind of retired lithium ion battery positive electrode material has a general formula xLi ₂ MnO ₃ ·(1-x)LiNO ₂ Wherein, the doping element N is at least one of metal elements Ni, co, mn, na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V, cr, fe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd and Sm, 0<x<1. In addition, a lithium-rich manganese-based material in which oxygen sites are doped with a non-metallic element such as F or S may also be included.

The waste manganese-containing material can be from waste zinc-manganese batteries and waste alkali-manganese batteries. The positive electrode material of the battery mainly comprises manganese dioxide powder (MnO) ₂ ) Carbon black, and the like, wherein the chemical valence of the manganese element is + 4.

The compound with the structure is easy to purchase in the market and low in cost, and meets the requirement of industrial production; in addition, the oxidized product of the compound with the structure is small in molecule and simple in structure, for example, a gas molecule can be removed as a byproduct through a gas-liquid separation method, and a compound with a low boiling point can be removed from a system through a distillation method or a reduced pressure distillation method.

The extraction of the powder of the anode material of the retired lithium ion battery can separate the powder of the anode material of the lithium ion battery from a current collector through the working procedures of disassembly, cracking, screening and the like; or after the decommissioned battery is disassembled, the powder of the lithium ion battery anode material is separated from the current collector in an organic solution soaking mode. The invention does not limit how to obtain the retired lithium ion battery anode material.

The method can also directly realize the recycling of the anode material without separating the anode material powder and the cathode material powder of the retired lithium ion battery. For example, the outer shell of the retired lithium ion battery is manually disassembled, and the single battery in the battery pack is taken out; discharging the single battery, and completely discharging; drying the single batteries, and placing the single batteries in a crusher for multistage crushing until the average diameter of crushed materials is less than 1 cm; drying the crushed material in a vacuum drying oven at 50-100 deg.c to recover volatile gaseous organic solvent, crushing the crushed material, sieving, and mixing the crushed material with the positive and negative pole material and adhesive. By adopting the method of the invention to reduce and leach the undersize, the metal elements in the anode material are leached out, and the cathode material and the binder are left in the slag.

Generally, when the retired lithium ion battery positive electrode material powder is extracted, residual electrolyte components such as lithium hexafluorophosphate in the retired lithium ion battery positive electrode material powder are also removed and recovered in a carbonate soaking or rinsing mode. The method for removing the residual components of the electrolyte in the cathode material of the retired lithium ion battery is not limited by the invention.

Generally, when extracting the lithium ion battery cathode material powder, drying the lithium ion battery cathode material waste powder to remove the residual organic solvent in the powder.

The acidic solution providing the reaction medium for the reductive leaching of manganese-containing materials may be a mineral acid, an organic acid or a mixture of an organic acid and a mineral acid. The amount of acid used is related to the molecular formula of the manganese-containing material waste. Generally, an excess of acid favors an increase in the leaching rate. However, neutralization of excess acid requires consumption of base and production of solid by-products such as sodium sulfate, ammonium sulfate. The amount of acid used is one of the main process parameters that must be optimized for a variety of different lithium ion battery cathode material waste materials.

The inorganic acid may be carborane acid (H [ CHB ] ₁₁ Cl ₁₁ ]) Hydrogen sulfuric acid (H) ₂ S), peroxycarbonic acid (H) ₂ CS ₄ ) Thiocarbonic acid (H) ₂ CS ₃ ) Hydrocyanic acid (HCN), selenocyanate (HSeCN), thiocyanic acid (HSCN), fluoroboric acid (HBF) ₄ ) Fluosilicic acid (H) ₂ SiF ₆ ) Hexafluorophosphoric acid (HPF) ₆ ) Hydrofluoric acid (HF), hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), and aluminum metaaluminate (HAlO) ₂ ) Tetrahydroxyaluminum (III) acid (HAl (OH) ₄ ) Arsenic acid (H) ₃ AsO ₄ ) Meta-arsenous acid (HAsO) ₂ ) Arsenous acid (H) ₃ AsO ₃ ) Jiao Shensuan (H) ₄ As ₂ O ₇ ) Boric acid (H) ₃ BO ₃ ) Metaboric acid ((HBO) ₂ ) _n ) Tetraboric acid (H) ₂ B ₄ O ₇ ) Perboric acid (HBO) ₃ ) Dodecatungstoboric acid (H) ₅ BW ₁₂ O ₄₀ ) Bromic acid (HBrO) ₃ ) Bromic acid (HBrO) ₂ ) Hypobromous acid (HBrO), and perbromic acid (HBrO) ₄ ) Ortho carbonic acid (H) ₄ CO ₄ ) Peroxydicarbonate (H2C) ₂ O ₆ ) Percarbonic acid (H) ₂ CO ₄ Or H ₂ CO ₃ ·H ₂ O ₂ ) Chloric acid (HClO 3), perchloric acid (HClO 4), chlorous acid (HClO) ₂ ) Hypochlorous acid (HClO), humic acid (HONC), cyanic acid (HOCN), isocyanic acid (HNCO), iodic acid (HIO) ₃ ) Hypoiodic acid (HIO or IOH), meta-periodic acid (HIO) ₄ ) Periodic acid (H) ₅ IO ₆ ) Burnt periodic acid (H) ₄ I ₂ O ₉ ) Nitric acid (HNO) ₃ ) Nitrous acid (HNO) ₂ ) Phosphoric acid (H3 PO) ₄ ) Orthophosphoric acid (H) ₅ PO ₅ ) Metaphosphoric acid (HPO) ₃ ) _n Phosphorous acid (H) ₃ PO ₃ ) Pyrophosphorous acid (H) ₄ P ₂ O ₅ ) Metaphosphoric acid (HPO) ₂ ) Hypophosphorous acid (H) ₃ PO ₂ ) Hypophosphorous acid (H) ₄ P ₂ O ₆ ) Pyrophosphoric acid (H) ₄ P ₂ O ₇ ) Sulfuric acid (H) ₂ SO ₄ ) "Ha" or "Ha" respectivelySulfuric acid (H) ₂ SO ₃ ) Thiosulfuric acid (H) ₂ S ₂ O ₃ ) Pyrosulfuric acid (H) ₂ S ₂ O ₇ ) Hyposulfuric acid (H) ₂ SO ₂ ) Polythionic acid (H) ₂ S _x O ₆ X = 2~6), orthosulfuric acid (H) ₆ SO ₆ ) Dithionous acid (H) ₂ S ₂ O ₄ ) Peroxymonosulfuric acid (H) ₂ SO ₅ ) Peroxodisulfuric acid (H) ₂ S ₂ O ₈ ) Chlorosulfonic acid (HSO) ₃ Cl), fluorosulfonic acid (HSO) ₃ F) Metasilicic acid (H) ₂ SiO ₃ Or SiO ₂ ·H ₂ O), orthosilicic acid (H) ₄ SiO ₄ ) Di-metasilicic acid (H) ₂ Si ₂ O ₅ Or 2SiO ₂ ·H ₂ O) and pyrosilicic acid (H) ₆ Si ₂ O ₇ Or 2SiO ₂ ·3H ₂ O), preferably any one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.

The organic acid may be at least one of oxalic acid, formic acid, acetic acid, propionic acid, succinic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, mandelic acid, methylsulfuric acid, ethylsulfuric acid, oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, bis (catechol) boric acid, bisoxaloboric acid, bismalonic acid, tris (pentafluoroethyl) trifluorophosphoric acid, triethyltrifluorophosphoric acid, tetracyanoboric acid, tartaric acid, malic acid, citric acid, ascorbic acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, salicylic acid and caffeic acid, and is preferably any one or more of oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid.

In the recovery process of the manganese-containing material powder, the solid-to-liquid ratio of the waste powder to the acidic solution containing the aldehyde compound may be 10 to 2000g/L, preferably 100 to 1000g/L, and more preferably 200 to 600g/L. Although the reaction can be accelerated by low solid-liquid ratio, and the leaching of metal elements is facilitated, the water consumption is large and insufficient; if the solid-to-liquid ratio is too high, the reaction may be incomplete and the metal elements may not be completely leached.

The reduction leaching of the manganese-containing material powder is carried out in an acidic solution containing an aldehyde compound, the usage amount of the aldehyde compound is related to the molecular formula of the lithium ion battery anode material powder, and the aldehyde compound is required by different lithium ion battery anode material powder in different amounts. The addition amount of the aldehyde compound is calculated according to the stoichiometric ratio according to the reaction formula of the aldehyde compound and the lithium ion battery anode material powder. A slight excess of aldehyde compound may be considered in order to ensure that the leaching reaction is carried out completely. After the reaction is completed, the excess aldehyde compound can be removed by distillation or distillation under reduced pressure. If the boiling point of the aldehyde compound is higher, the aldehyde compound is not easy to remove by a distillation or reduced pressure distillation method, and the proper excess of the powder of the anode material of the retired lithium ion battery can be considered.

In the recovery process of the manganese-containing material powder, the reaction temperature can be controlled to be 0-100 ℃, preferably 25-99 ℃, and further preferably 45-95 ℃. Generally, the reductive leaching reaction is an exothermic reaction, and the maintenance of the reaction consumes less energy. If the reaction exotherm is significant, the rate of addition of the aldehyde compound is controlled, preferably in portions, or a temperature reduction is applied.

In the process of recovering the manganese-containing material powder, the reaction time may be controlled to be 0.1 to 12 hours, preferably 1 to 6 hours, and more preferably 2 to 4 hours. The reaction rate is high, the reaction can be completed in a short time, and the reaction time is generally prolonged appropriately to ensure the completion of the reaction.

The reduction leaching reaction is carried out under stirring, and the stirring manner and the stirring speed are not particularly limited.

The reaction equipment used for the reduction leaching reaction can use all applicable containers and pressure containers in principle, the material of the container needs to be selected according to the physicochemical properties of reactants, and the material with acid resistance is preferably adopted. The manganese-containing material powder (in Mn) _x M _y O _z Simply expressed, M represents other metal elements than manganese) may be carried out batchwise, semi-continuously or continuously. As is clear from the reaction equation (reaction formula (1)), the reductive leaching may produce CO as a by-product ₂ . With the continuous progress of the reaction, CO ₂ Is increasing in amount, and results in the reverseShould the pressure in the container rise continuously. Considering safe production and reducing the manufacturing cost of the equipment, it is possible to control the reaction rate by slowly adding a certain reactant while releasing CO ₂ So that the pressure in the reaction vessel is stabilized at a certain level.

Mn _x M _y O _z + (2z-4)H ⁺ +HCHO xMn ²⁺ + yM ²⁺ + CO ₂ + (z-1)H ₂ O (1)

After the reaction is completed, unreacted reactants or reaction byproducts can be removed by means of distillation, reduced pressure distillation and the like; or the next process can be continued without any treatment.

After leaching liquid and filter residue are obtained, the method also comprises the following steps: washing the filter residue for multiple times to obtain a washing liquid and washing the filter residue, and mixing the washing liquid with the leaching solution. After the washing filter residue is accumulated to a certain amount, carrying out secondary reaction on the washing filter residue and an acidic solution containing an aldehyde compound, stirring and heating, carrying out solid-liquid separation after reaction to obtain a secondary leaching solution and secondary reaction filter residue, and leaching metal elements in the washing filter residue.

The method for recovering the manganese-containing material is further described below by way of specific examples.

Example 1

A21 Ah soft package battery (used for an electric automobile) is taken, and the discharge capacity of the soft package battery is tested and found to be attenuated to 80% of the rated capacity, so that the service life is considered to be finished. The chemical composition of the positive active material of the batteries in this batch was LiNi according to the cell design report _0.6 Co _0.2 Mn _0.2 O ₂ . The method comprises the steps of disassembling the battery after the battery is soaked in saline water and discharged, dissolving out electrolyte remained in a pole piece in a solvent soaking mode, drying the pole piece in an oven, and separating anode material powder from an aluminum current collector in a high-temperature cracking mode. The anode material powder is mixed with a conductive carbon material, a binder and the like.

Preparing 50 mass percent of sulfuric acid solution, adding 5 mass percent of excessive formaldehyde (37 percent of formaldehyde aqueous solution) calculated according to a chemical reaction formula, and weighing 1000mL of the acid solution in a container; 500.0g of waste cathode material powder is weighed and slowly added into the container, and the solid-liquid ratio is about 500g/L. Starting stirring and heating the reaction container in a water bath, wherein the temperature of the water bath is 90 ℃, and cooling after reacting for 2 hours. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of metal elements such as nickel, cobalt, manganese, lithium and the like by ICP-OES, and calculating the leaching rate of each metal element, wherein the results are respectively as follows: 99.2 percent of Ni; co,99.1%; 99.3 percent of Mn; li,99.6%. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

After the first leaching is carried out, if the acid and the reducing agent in the leaching solution have the surplus, the leaching solution can be continuously used for leaching the next batch of manganese-containing materials.

Example 2

A21 Ah soft package battery (used for an electric automobile) is taken, and the discharge capacity of the soft package battery is tested and found to be attenuated to 80% of the rated capacity, so that the service life is considered to be finished. According to the cell design report, the chemical composition of the positive active material of the batch of batteries was LiNi _0.6 Co _0.2 Mn _0.2 O ₂ . The method comprises the steps of disassembling the battery after the battery is soaked in saline water and discharged, dissolving out electrolyte remained in a pole piece in a solvent soaking mode, drying the pole piece in an oven, and separating anode material powder from an aluminum current collector in a high-temperature cracking mode. The anode material powder is mixed with a conductive carbon material, a very small amount of binder and the like.

100.0g of waste positive electrode material powder was weighed and charged into a reaction vessel. Preparing a sulfuric acid solution with the mass percentage of 30%, and adding a reducing agent formaldehyde (37% formaldehyde aqueous solution), wherein the mass percentage of the reducing agent formaldehyde is about 4.6%. And slowly adding an acidic solution containing a reducing agent into the reaction vessel, wherein the solid-liquid ratio is about 200g/L. And simultaneously starting stirring and heating the reaction container, wherein the reaction temperature is 75 ℃, and cooling after reacting for 12 hours. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of metal elements such as nickel, cobalt, manganese, lithium and the like by ICP-OES, and calculating the leaching rate of each metal element, wherein the results are respectively as follows: 98.2 percent of Ni; co,98.8%; 99.3 percent of Mn; and Li,99.7%. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

Example 3

Several pieces of retired lithium ion secondary batteries are used, the batteries basically lose efficacy, the discharge capacity is almost zero, and the electrochemical systems of the batteries in the batch are different. The chemical formula of the main positive active material of a part of batteries is LiNi _0.5 Co _0.2 Mn _0.3 O ₂ The chemical formula of the main positive active material of part of the battery is LiMn ₂ O ₄ . The method comprises the steps of dismantling the battery after the battery is soaked in saline water and discharged, dissolving out electrolyte remained in a pole piece in a solvent soaking mode, drying the pole piece in an oven, and then pyrolyzing a binder in the pole piece to obtain a mixture of powder materials of two lithium ion battery positive material wastes (mixed conductive carbon materials). Sampling, and analyzing the contents of elements such as nickel, cobalt, manganese, lithium and the like in the mixed powder by ICP-OES.

Preparing 50 mass percent of sulfuric acid solution, and adding a reducing agent acetaldehyde, wherein the mass percent of the reducing agent is 10.0%. Measuring 100mL of acid solution containing a reducing agent in a container; 100.0g of waste cathode material powder is weighed and slowly added into the container, and the solid-liquid ratio is about 1000g/L. Starting stirring and heating the reaction vessel in a water bath at 45 ℃, reacting for 1 hour, and cooling. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of metal elements such as nickel, cobalt, manganese, lithium and the like by ICP-OES, and calculating the leaching rate of each metal element, wherein the results are respectively as follows: the results were respectively: ni,66.9%; co,65.6%; mn,63.6%; li,85.0%.

And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

Example 4

The chemical formula of the anode material cannot be determined by taking a plurality of waste lithium ion secondary batteries. The method comprises the steps of dismantling the battery after the battery is soaked in salt water and discharged, dissolving out electrolyte remained in a pole piece in a solvent soaking mode, drying the pole piece in an oven, pyrolyzing a binder in the pole piece to obtain powder (mixed conductive carbon material) of the lithium ion battery anode material waste, sampling, and analyzing the content of elements such as nickel, cobalt, manganese, lithium, aluminum, zirconium, yttrium, iron and the like in the mixed powder by ICP-OES.

Preparing a 50% sulfuric acid solution by mass, adding a reducing agent formaldehyde (37% formaldehyde aqueous solution) by mass, wherein the mass percentage of the formaldehyde is about 5.3%, and measuring 1000mL of the solution in a container; 500.0g of powder of the lithium ion battery anode material waste is weighed and slowly added into the container, and the solid-to-liquid ratio is about 500g/L. Starting stirring and heating the reaction container in water bath, wherein the reaction temperature is 90 ℃, and cooling after reacting for 1 hour. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of metal elements such as nickel, cobalt, manganese, lithium and the like by ICP-OES, and calculating the leaching rate of each metal element, wherein the results are respectively as follows: 99.4 percent of Ni; co,98.5%; 99.1% of Mn; li,99.5%.

Example 5

Taking a No. 5 alkaline manganese battery with exhausted electric quantity in a plurality of household appliances and toys, cutting the battery, removing a shell and a negative electrode, and collecting black powder. Washing the black powder with water, filtering and drying the powder.

10.0g of waste positive electrode material powder was weighed and charged into a reaction vessel. 1L of acetic acid is measured, and a reducing agent formaldehyde (37% formaldehyde aqueous solution) is added, wherein the mass percentage of the reducing agent formaldehyde is about 4.6%. And slowly adding an acidic solution containing a reducing agent into the reaction vessel, wherein the solid-liquid ratio is about 200g/L. And simultaneously starting stirring and heating the reaction container, wherein the reaction temperature is 65 ℃, and cooling after reacting for 24 hours. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of the manganese element by ICP-OES, and calculating the leaching rate of each element of manganese, wherein the result is as follows: 75.1 percent. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

Example 6

Taking a No. 5 alkaline manganese battery with exhausted electric quantity in a plurality of household appliances and toys, cutting the battery, removing a shell and a negative electrode, and collecting black powder. The black powder was washed with water, filtered and dried to powder.

10.0g of waste positive electrode material powder was weighed and charged into a reaction vessel. Preparing a 50 mass percent sulfuric acid solution, and adding a reducing agent propionaldehyde, wherein the mass percent of the reducing agent is about 10 percent. And slowly adding an acidic solution containing a reducing agent into the reaction vessel, wherein the solid-to-liquid ratio is about 500g/L. And simultaneously starting stirring and heating the reaction container, wherein the reaction temperature is 45 ℃, and cooling after reacting for 12 hours. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of the manganese element by ICP-OES, and calculating the leaching rate of the manganese element, wherein the result is as follows: 90.6 percent. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

After the first leaching is carried out, if the acid and the reducing agent in the leaching solution have the rest, the leaching solution can be continuously used for leaching the next batch of manganese-containing materials.

Example 7

Taking a plurality of lithium manganese disposable button batteries, cutting the batteries, removing the shell and the negative electrode, and collecting the powder of the positive electrode. Cleaning the black powder with organic solvent, removing electrolyte, filtering and drying the powder.

2.0g of waste positive electrode material powder was weighed and charged into a reaction vessel. Preparing 50% of sulfuric acid solution by mass percent, and adding a reducing agent formaldehyde, wherein the mass percent of the reducing agent is about 3.3%. And slowly adding an acidic solution containing a reducing agent into the reaction vessel, wherein the solid-to-liquid ratio is about 500g/L. And simultaneously starting stirring and heating the reaction container, wherein the reaction temperature is 95 ℃, and cooling after reacting for 1 hour. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue. Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of the manganese element by ICP-OES, and calculating the leaching rate of the manganese element, wherein the result is as follows: 99.6 percent. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

Example 8

Taking several 15Ah hard shell batteries, the discharge capacity of the batteries is tested and found to be attenuated to 70% of the rated capacity, and the service life is considered to be finished. According to the cell design report, the chemical composition of the positive active material of the batch of batteries is LiMn ₂ O ₄ . The battery is disassembled after the battery is soaked in the saline water and discharged, the battery is dried and placed in a crusherPerforming multistage crushing in the crusher until the average diameter of crushed materials is less than 1 cm; drying the crushed material in a vacuum drying oven at 70 deg.C, condensing and recovering volatile gaseous organic solvent molecules, further crushing the dried agglomerated crushed material, sieving, wherein the sieved material is a mixture of positive and negative electrode materials of lithium ion battery and binder, and the sieved material is a mixture of the outer package of the single battery, copper foil and aluminum foil. Taking undersize, weighing 100.0g of powder, and adding into a reaction container. Preparing a sulfuric acid solution with the mass percentage of 30%, and adding a reducing agent formaldehyde (37% formaldehyde aqueous solution), wherein the mass percentage of the reducing agent is about 8%. And slowly adding an acidic solution containing a reducing agent into the reaction vessel, wherein the solid-to-liquid ratio is about 200g/L. And simultaneously starting stirring and heating the reaction vessel, wherein the reaction temperature is 90 ℃, and cooling after reacting for 6 hours. Filtering to realize solid-liquid separation, and respectively obtaining leachate and filter residue (comprising unreacted negative electrode material powder, conductive agent, binder and the like). Washing the filter residue for several times, collecting the washing liquid and mixing with the leaching solution. Taking a liquid phase sample, analyzing the concentration of metal elements such as nickel, cobalt, manganese, lithium and the like by ICP-OES, and calculating the leaching rate of each metal element, wherein the results are respectively as follows: 99.8 percent of Mn; li,99.6%. And collecting the filtered filter residue, accumulating to a certain amount, and reducing and leaching again.

In conclusion, the reducing agent adopted by the invention has high reaction activity, can reduce the high-valence insoluble metal ions in the waste manganese-containing material into low-valence soluble ions, and the by-products after the reaction are gases or low-boiling-point micromolecule organic matters and are easy to remove from the system; the leaching recovery process has short route and low cost, can leach the metal ions in the waste materials through one-step reaction, and has high leaching rate and short leaching time.

In a second aspect of the embodiments of the present invention, a method for regenerating a manganese-containing material is provided, which takes a positive electrode material of a lithium ion battery as an example, and includes the following five steps.

(1) Recovery of the cathode material waste: and treating the lithium ion battery anode material waste according to the method for recovering the lithium ion battery anode material waste to obtain leachate and filter residue. The method for recycling the lithium ion battery cathode material waste is described above, and is not described herein again.

(2) Preparing a precursor solution: and adjusting the content of each metal element in the leachate according to the element composition and content in the leachate to ensure that the molar ratio of each metal element is consistent with the chemical formula of the target cathode material, thereby obtaining a precursor solution.

The target cathode material may have a chemical formula of Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O ₂ 、Li _1+η [Mn _2-a Mˊ _a ]O ₄ Or xLi ₂ MnO ₃ ·(1-x)LiNO ₂ . And adjusting the content of each metal element in the leaching solution according to the chemical formula of the target cathode material to obtain a precursor solution, wherein the concentration range of the precursor solution is generally 0.5-3 mol/L. Generally, water-soluble salts of nickel, cobalt or/and manganese are added to the leachate; if the precursor is doped with metal ions, one or more than two of M, M' or N water-soluble salts are added. The doping element M, M' or N is any one of metal elements Ni, co, mn, na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V, cr, fe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd, and Sm.

Preferably, the anion of the water-soluble salt is a chloride ion, a sulfate ion, a nitrate ion, an oxalate ion, a hydrogen phosphate ion, a dihydrogen phosphate ion, or an acetate ion. Generally, the anion of the water-soluble salt is preferably identical to the anion of the acid in the leach solution. Sulfate ions are preferred from the viewpoint of cost saving.

(3) Preparing a target positive electrode material precursor: and preparing a target anode material precursor by using the precursor solution in a precursor preparation process, and simultaneously obtaining a lithium ion-containing solution.

The preparation method of the target cathode material precursor can be a coprecipitation method.

The coprecipitation method comprises the following steps: and adding an ammonia water solution and/or an alkaline water solution into the precursor solution, carrying out coprecipitation reaction on metal ions except lithium, and carrying out solid-liquid separation to obtain a target anode material precursor and a lithium ion-containing solution respectively. Inert gas or nitrogen can be introduced for protection in the reaction process so as to prevent the core metal elements from being oxidized and influencing the tap density of the material.

Wherein, the ammonia water solution can be an aqueous solution containing at least one of ammonia, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate and ammonium sulfate, and the concentration is 0.1-1 mol/L; the aqueous alkali solution may be an aqueous solution containing at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydrogencarbonate, and has a concentration of 0.5 to 5 mol/L.

The pH value of the mixed solution is 9-12.5, the reaction temperature is 30-80 ℃, the stirring speed is 100-2000 rpm, and the reaction time is 1-24 hours. The reaction temperature is preferably controlled to be about 50 ℃, the production efficiency and the material performance are considered, and the reaction time is preferably controlled to be 2-12 hours.

When the aqueous ammonia solution is an aqueous solution of a hydroxide or the aqueous alkaline solution is an aqueous solution of a hydroxide, the precursor from which the target positive electrode material is obtained is a composite hydroxide, and the precursor can be represented by the general formula [ Ni, for example [ ] _1-x-y-z Co _x Mn _y M _z ](OH) ₂ And (4) showing. If the aqueous ammonia solution is an aqueous solution of ammonium carbonate or the aqueous alkaline solution is an aqueous solution of sodium carbonate, the precursor for producing the positive electrode material of the present invention is a composite carbonate, and may be represented by the general formula [ Ni, for example ] _1-x-y-z Co _x Mn _y M _z ]CO ₃ And (4) showing. Filtering, washing and drying the composite compound to prepare a precursor of the target cathode material or heat-treating the composite hydroxide compound to obtain the corresponding composite oxide. The water or CO in the composite hydroxide compound can be removed by heat treatment ₂ . The heat treatment temperature is preferably 400 to 1000 ℃ and the heat treatment time is preferably 0.5 to 10 hours.

(4) And recovering lithium element in the liquid phase to obtain the lithium source compound.

The method for recovering lithium element in liquid phase includes introducing carbon dioxide or adding carbonate, phosphate and fluoride salt into lithium ion containing solution. And further processing the recovered lithium salt into hydroxide for preparing the cathode material or other lithium battery materials or directly using the hydroxide for preparing the cathode material.

The lithium source compound may be at least one of a lithium hydroxide, a lithium oxyhydroxide, a lithium oxide, a lithium sulfide, a lithium carbonate, a lithium nitrate, a lithium acetate, and a lithium halide. The lithium source compound may be one or more of lithium hydroxide (or lithium hydroxide containing water of crystallization), lithium carbonate, lithium nitrate, lithium acetate, and lithium fluoride, and lithium carbonate or lithium hydroxide is generally preferred.

As a preferred scheme, the firing can be performed for 1 to 24 hours at the temperature of between 300 and 800 ℃ and then for 1 to 24 hours at the temperature of between 700 and 1050 ℃; the roasting atmosphere during roasting is air or an oxidizing atmosphere with oxygen content more than 30%.

The target positive electrode material can also be modified by various methods in order to optimize the performance of the material. For example, step (5) is followed by the steps of: the target cathode material is coated with the Lewis base compound on the outer surface, and the method comprises a solid phase mixing method, a liquid phase chelating method and the like. For example, a lewis base compound is mixed with a target positive electrode material by a mechanical method and heat-treated, and dot coating is performed on the outer surface of the material. For another example, the lewis base compound is coated on the outer surface by a method of chemically reacting a metal alkyl oxide with a hydroxyl group on the surface of the positive electrode material.

The method for recycling the waste material of the positive electrode material of the lithium ion battery is further described by the following specific examples.

Based on the leachate recovered in example 1, the content of each metal element in the leachate was calculated based on the concentration of the metal element such as nickel, cobalt, manganese and the like in example 1, and the content was calculated according to the chemical formula [ Ni [ ] _0.6 Co _0.2 Mn _0.2 ](OH) ₂ Regulating and controlling the content of each metal element in the solution. To dippingAdding nickel sulfate, cobalt sulfate or manganese sulfate into the effluent, and adjusting the concentration of each metal element by controlling the amount of added water to obtain a precursor solution for preparing the target cathode material. If other impurity elements exist in the leachate, impurity removal treatment is firstly carried out.

Introducing N into the reactor ₂ Bubbling to remove air and make the whole reaction process in N ₂ Is carried out in an atmosphere. Herein N ₂ May be replaced with a noble gas. And respectively introducing the precursor solution, the ammonia water solution and the alkaline water solution into the reactor, and simultaneously starting stirring. The alkali water solution is sodium hydroxide water solution with the concentration of 4 mol/L, the pH value of the solution is adjusted to be 9-12 in the reaction process, the pH value is higher in the early nucleation stage, and the pH value is lower in the later particle growth stage. The reaction temperature is controlled to be about 50 ℃, and the reaction time is about 12 hours. Filtering and washing to obtain precursor composite hydroxide and filtrate containing lithium.

And introducing carbon dioxide into the lithium-containing filtrate, recovering lithium carbonate crystals, filtering and drying.

And drying the precursor composite hydroxide. The precursor and lithium carbonate were weighed in a molar ratio of 1.02, mixed using a dry process, and then transferred to a tube furnace for firing in an air atmosphere. And after the sintering, cooling the anode material to room temperature in a furnace, and crushing the anode material after discharging to obtain the target anode material.

The obtained target positive electrode material was evaluated using a coin cell. Mixing the prepared positive electrode material, conductive agent acetylene black and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 80. The slurry was coated on an aluminum foil having a thickness of 20 μm, and then vacuum-dried at 120 ℃, and punched into a circular sheet having a diameter of about 14 mm, to prepare a positive electrode. Using a metallic lithium sheet as a negative electrode, an electrolyte solvent composition DMC/EC/EMC =1 (volume ratio), lithium salt-containing LiPF ₆ 1.0 And (3) mol/L, assembling the diaphragm which is a porous polyethylene film and has the thickness of 20 mu m into a 2025 type button cell in an Ar gas-protected glove box.

The electrochemical properties of the obtained button cell are as follows: the first discharge capacity was 175mAh/g, the first discharge efficiency was 89%, and the cycle capacity retention rate (room temperature, 0.2C,100 weeks) was 96.5%.

Based on the leachate recovered in example 2, the contents of the respective metal elements in the leachate were calculated based on the concentrations of the metal elements such as nickel, cobalt, manganese and the like in Table 1, and the contents were calculated according to the chemical formula [ Ni ] _0.6 Co _0.2 Mn _0.2 ](OH) ₂ Regulating and controlling the content of each metal element in the solution. Adding nickel sulfate, cobalt sulfate or manganese sulfate into the leachate, and adjusting the concentration of each metal element by controlling the amount of added water to obtain a precursor solution. If other impurity elements exist in the leachate, impurity removal treatment is firstly carried out.

Introducing N into the reactor ₂ Bubbling to remove air and make the whole reaction process in N ₂ Is carried out in an atmosphere. Herein N ₂ May be replaced with a noble gas. Respectively introducing a precursor solution for preparing the target anode material, an ammonia water solution and an alkaline water solution into the reactor, and simultaneously starting stirring. The alkali water solution is sodium hydroxide water solution with the concentration of 4 mol/L, the pH value of the solution is adjusted to be 9-12 in the reaction process, the pH value is higher in the early nucleation stage, and the pH value is lower in the later particle growth stage. The reaction temperature is controlled to be about 50 ℃, and the reaction time is about 12 hours. Filtering and washing to obtain precursor composite hydroxide and filtrate containing lithium.

And adding ammonium carbonate into the lithium-containing filtrate, recovering lithium carbonate crystals, filtering and drying.

And drying the precursor composite hydroxide. The precursor and lithium carbonate were weighed in a molar ratio of 1:1.05, mixed using a dry process, and then transferred to a tube furnace for firing in an air atmosphere. And after the sintering, cooling the anode material to room temperature in a furnace, and crushing the anode material after discharging to obtain the target anode material.

The obtained cathode material has a chemical formula of LiNi as a main chemical component _0.5 Co _0.25 Mn _0.25 O ₂ The electrochemical properties are as follows: the first discharge capacity was 165mAh/g, the first discharge efficiency was 89%, and the cycle capacity retention rate (room temperature, 0.2C,100 weeks) was 97%.

In addition to the anode material of the retired power lithium ion secondary battery, manganese is containedThe material also comes from the anode material of waste zinc-manganese battery, waste alkali-manganese battery and waste lithium-manganese primary battery, and the material is characterized in that the manganese element mainly adopts MnO ₂ Exist in the form of (1).

In a third aspect of the embodiments of the present invention, a method for regenerating a manganese-containing material is provided, which takes the positive electrode materials of a waste zinc-manganese battery, a waste alkali-manganese battery, and a waste lithium-manganese primary battery as examples, and includes the following steps:

(1) Recovery of manganese-containing materials: treating the manganese-containing material waste according to any one of the above-described manganese-containing material recovery methods to obtain leachate and filter residue;

(2) Preparing electrolytic manganese dioxide electrolyte: adjusting the contents of the components (mainly MnSO) in the leachate according to the element composition and content in the leachate ₄ And H ₂ SO ₄ ) Making the composition of the leachate consistent with the electrolytic solution of electrolytic manganese dioxide to obtain an electrolyte solution; generally, the electrolyte composition is: mnSO ₄ 100～140 g/L，H ₂ SO ₄ 30～50 g/L。

(3) Electrolysis: heating the electrolyte solution to 90-95 ℃, and sending the electrolyte solution to an electrolytic cell, wherein the anode of the electrolytic cell is a titanium-based manganese alloy plate or strip, and the electrolysis conditions are as follows: the cell voltage is 2-3V, the electrolysis temperature is 95-98 ℃, and the anode current density is 60-70A/m ² The electrolysis period is 10 to 12 days, and a mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product is obtained after electrolysis; the electrolysis reaction formula is as follows:

MnSO ₄ + 2H ₂ O MnO ₂ + H ₂ SO ₄ + H ₂

(4) Rinsing: crushing the mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product into particles with the particle size of 20-40 mm, then putting the particles into a rinsing tank for rinsing, and adopting four-stage rinsing processes of water washing, alkali washing, backwashing and water washing, wherein the water washing and backwashing temperature is 90-95 ℃, the alkali washing temperature is 55-70 ℃, and the rinsing period is 29-34 h;

(6) Mixing for 16-24 h to obtain the electrolytic manganese dioxide product which can be used for acid zinc-manganese batteries, alkaline manganese batteries and lithium-manganese primary batteries and can also be used for preparing the anode material lithium manganate of lithium ion batteries.

The method for regenerating the alkaline manganese cell cathode waste material is further described by the following specific examples.

Based on the leachate recovered in example 7 (several grams of manganese-containing material waste are added and a second leach is conducted to ensure removal of residual reductant from the leachate and a second filtration to remove the residue to produce a leachate), the manganese dioxide electrolyte is adjusted, according to the results of the analysis, to have a composition: mnSO ₄ Has a concentration of 120 g/L, H ₂ SO ₄ Has a concentration of 30 g/L. Sending to an electrolytic cell, heating the electrolyte to 95 ℃, adjusting the voltage of the electrolytic cell, setting the current density of the anode, and starting electrolysis. And after the electrolysis, taking down the manganese dioxide semi-finished product, rinsing, grinding and other processes, and analyzing by an XRD instrument, an SEM instrument and other instruments.

Based on the closed-loop circulation of metal elements, the main metal elements in the manganese-containing material can be recovered and regenerated by the technology, the application range is wide, the anode material of the retired lithium ion secondary battery can be recovered and regenerated, the anode material comprises a layered structure, a spinel structure, polyanions and other anode materials, the anode material of the waste zinc-manganese battery, the waste alkali-manganese battery and the waste lithium-manganese primary battery can be recovered, and the failed manganese catalyst and manganese adsorbent can be recovered and regenerated. Wherein the regeneration method of the ion sieve manganese adsorbent also adopts an electrolysis method.

Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims

1. The method for recovering manganese element from the manganese-containing material is characterized by comprising the following steps of:

reacting a manganese-containing material with an acidic solution containing an aldehyde compound, and performing solid-liquid separation on a reactant after the reaction to obtain a leaching solution and filter residues for leaching manganese metal elements in the manganese-containing material, wherein the manganese-containing material contains the manganese elements, the chemical valence of the manganese is at least one valence of +3 valence, +4 valence or +6 valence, and the molecular structural formula of the aldehyde compound is as follows:

2. The method for recovering manganese element from a manganese-containing material according to claim 1, wherein R in the molecular structural formula of the aldehyde compound is hydrogen or an alkyl group having 1 to 5 carbon atoms.

3. The method for recovering manganese element from manganese-containing materials according to claim 1, wherein the aldehyde compound is one or more of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-valeraldehyde, 2-methylpropionaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 2,2-dimethylpropionaldehyde.

4. The method for recovering manganese element from manganese-containing material according to claim 1, wherein the solid-to-liquid ratio of manganese-containing material to acidic solution containing aldehyde compound is 10-2000 g/L, the reaction temperature is 20-100 ℃, and the reaction time is 0.1-36 hours.

5. The method for recovering manganese element in manganese-containing material according to claim 1, wherein said acidic solution is any one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and/or organic acid, wherein said organic acid is any one or more of oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid and valeric acid.

6. The method for recovering manganese in manganese-containing materials according to claim 1, further comprising the steps of, after obtaining leachate and filter residue: washing the filter residue for a plurality of times to obtain washing liquid and washing filter residue, mixing the washing liquid with the leaching liquid, reacting the washing filter residue with an acid solution containing aldehyde compounds, stirring and heating, carrying out solid-liquid separation after reaction to obtain a secondary leaching liquid and a secondary reaction filter residue, and leaching metal elements in the washing filter residue.

7. A method for regenerating a manganese-containing material, wherein the manganese-containing material is a positive electrode material of an ex-service power lithium ion secondary battery, is characterized by comprising the following steps:

(1) Recovery of manganese-containing materials: the method of recovering manganese-containing materials according to any one of claims 1 to 6, obtaining a leach liquor and a residue;

(3) Preparing a target positive electrode material precursor: preparing the precursor solution into a target anode material precursor by a coprecipitation method preparation process, and simultaneously obtaining a lithium ion-containing solution;

8. The method according to claim 7, wherein in the step (2), the chemical formula of the target cathode material is Li _1+δ [Ni _1-x-y-z Co _x Mn _y M _z ]O ₂ 、Li _1+η [Mn _2-a Mˊ _a ]O ₄ Or xLi ₂ MnO ₃ ·(1-x)LiNO ₂ Adding one or more of water-soluble salts of nickel, cobalt and manganese and M, M 'or N to the leachate to adjust the content of each metal element In the leachate according to the chemical formula of the target cathode material, wherein the doping element M, M' or N is any one or more of metal elements Ni, co, mn, na, K, mg, ca, sr, ba, al, ga, in, ge, sn, ti, V, cr, fe, cu, zn, Y, zr, nb, mo, cd, W, la, ce, nd and Sm.

9. The method of claim 8, wherein the water-soluble salt has an anion selected from the group consisting of chloride, sulfate, nitrate, oxalate, hydrogen phosphate, dihydrogen phosphate, and acetate.

10. A method according to claim 9, wherein the anions of the water soluble salts correspond to the anions of the acid in the leach solution.

11. The method for regenerating a manganese-containing material according to claim 7, wherein said coprecipitation method comprises the steps of: and adding an ammonia water solution and/or an alkali water solution into the precursor solution, carrying out coprecipitation reaction on metal ions except lithium, and carrying out solid-liquid separation to obtain a target positive electrode material precursor and a lithium ion-containing solution respectively.

12. The method of claim 11, wherein the aqueous solution of ammonia is an aqueous solution containing at least one of ammonia, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate and ammonium sulfate, and the concentration of the aqueous solution is 0.1 to 1 mol/L.

13. The method according to claim 11, wherein the aqueous alkali solution is an aqueous solution containing at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and has a concentration of 0.5 to 5 mol/L.

14. The method for recycling manganese-containing materials according to claim 7, further comprising the step after said step (5): and carrying out doping and/or coating modification on the target positive electrode material.

15. A method for regenerating a manganese-containing material, wherein said manganese-containing material is a positive electrode material for an alkaline manganese battery, comprising the steps of:

(1) Recovery of manganese-containing materials: a leach solution and a residue obtained by the method according to any one of claims 1 to 8;

(3) Electrolysis: heating the electrolyte solution to 80-98 ℃, sending the electrolyte solution to an electrolytic cell, wherein the anode of the electrolytic cell is a titanium-based manganese alloy plate or strip, and electrolyzing to obtain a mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product;

(4) Rinsing: crushing a mercury-free alkali manganese type electrolytic manganese dioxide semi-finished product into manganese dioxide powder with the particle size of 20-40 mm, putting the manganese dioxide powder into a rinsing tank for rinsing, and sequentially carrying out four-stage rinsing processes of water washing, alkali washing, backwashing and water washing, wherein the water washing temperature and the backwashing temperature are 90-95 ℃, the alkali washing temperature is 55-70 ℃, and the rinsing period is 29-34 hours;

(6) Mixing to obtain the electrolytic manganese dioxide product which can be used for the alkaline manganese battery, wherein the mixing time is 16-24 h.

16. The method for regenerating a manganese-containing material according to claim 15, wherein in the step (3) of electrolysis, the electrolysis conditions are as follows: the electrolysis temperature is 95-98 ℃, the anode current density is 60-70A/m 2, the electrolyte sulfuric acid concentration is 30-50 g/L, and the electrolysis period is 10-12 days.