CN104868190B - The leaching of metal and recovery method in a kind of lithium ion cell anode waste - Google Patents
The leaching of metal and recovery method in a kind of lithium ion cell anode waste Download PDFInfo
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- CN104868190B CN104868190B CN201510242788.1A CN201510242788A CN104868190B CN 104868190 B CN104868190 B CN 104868190B CN 201510242788 A CN201510242788 A CN 201510242788A CN 104868190 B CN104868190 B CN 104868190B
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Abstract
The invention provides a kind of leaching of metal in lithium ion cell anode waste and recovery method.The leaching method is：Lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent, separation of solid and liquid is carried out after reaction, leachate and filter residue is obtained, the leaching of metal in lithium ion cell anode waste is realized.Based on this leaching method, the invention provides a kind of recovery method of the lithium ion cell anode waste based on metal closed loop cycle.The leaching rate of the leaching method metal of metal is high in the lithium ion cell anode waste, extraction time is short, processing cost is low, applied widely, it is to avoid secondary pollution and the in the prior art Complicated Flow to various metal progress separating-purifyings in leachate；The recovery method technological process of the lithium ion cell anode waste based on metal closed loop cycle is short, and the closed loop cycle for realizing metal is utilized.
Description
Technical field
Recycled the invention belongs to secondary resource and recycling economy technical field, be related to a kind of lithium ion cell positive and give up
The leaching method of metal in material, more particularly to a kind of lithium ion cell positive based on the nickeliferous of metal closed loop cycle, cobalt or manganese
The controllable leaching method and recovery method of metals from waste.
Background technology
With extensive use of the lithium ion battery in portable type electronic product, the yield and demand of lithium ion battery are acute
Increase, from 2000 to 2010, the global annual production of lithium ion battery added 800%.Because lithium ion battery is in electric automobile
With the further application in intelligent grid, its demand can still be increased considerably for 10 years in future.South Korea in 2013, Japan and in
State's lithium ion battery yield accounts for more than the 90% of global yield.At present, China has become the largest production of lithium ion battery, disappeared
Take and one of exported country.
Due to electronic product update speed it is more and more faster, in addition lithium ion battery life-span typically only 1~3
Year, therefore, the waste material produced in substantial amounts of waste lithium ion and its production process will be produced in the coming years.One side
In face, these discarded objects containing poisonous and hazardous heavy metal and with extremely strong toxicity and corrosive organic electrolyte (such as
LiFP6), such as deal with improperly, it will serious threat is caused to ecological environment and health；On the other hand, in these discarded objects
Containing valuable metals such as nickel, cobalt, manganese, lithium, copper and aluminium, wherein cobalt and lithium is considered as strategy metal, in following sustainable material
Occupied an important position in material and technology.And according to statistics (the USGS World Mine of United States Geological Survey
Production and Reserves 2013), the nickel of China, cobalt, the mineral resources of manganese and lithium only account for global reserves
4.01%th, 1.07%, 7.02% and 26.99%, these lithium ion batteries production needed for metal imbalance between supply and demand in China
Through increasingly protruding.Therefore, if can high efficiente callback used Li ion cell and its production waste material in metal, it can not only be avoided
To environment and the risk of human health, and the metal that replacement is provided can be produced for lithium ion battery, reduced to external metal
The interdependency of resource, promotes sustainable development and the industrial upgrading of lithium ion battery industry.
At present, both at home and abroad in terms of used Li ion cell recycling recovery still in starting and developing stage, recovery method
Mainly include hydrometallurgy, pyrometallurgy and biological metallurgy technology.Because hydrometallurgical technology has, the rate of recovery of metal is high, return
The high and low energy consumption of purity and low toxic and harmful gas of product are received the advantages of discharge, it is considered to be reclaim used Li ion cell and its
Produce the applicable technology of waste material.Due to can be by metal effectively from solid phase is transferred to the aqueous solution, acidic leaching be in hydrometallurgy
Occupy indispensable status in technology.Existing hydrometallurgical processes are mainly for LiCoO2For the useless of positive active material
The recovery of lithium ion battery, correlative study is concentrated mainly on the optimization to extract technology to realize the high leaching rate of cobalt and lithium.For
Follow-up impurity removal process caused by dissolving due to aluminium foil is avoided, before lithium ion cell anode waste enters acidleach, is led to
Some pre-treatment steps are often needed to separate positive electrode from aluminium foil, such as patent CN101942569B, CN
NaOH solution dissolving, ultrasonic wave cleaning, N- methyl is respectively adopted in 101318712B, CN 102382987B and CN 100440615C
The processing of pyrrolidones (NMP) ultrasonic wave added and NMP stirring immersion separation positive electrodes and aluminium foil.These complicated pretreating process
On the one hand make it that whole technological process is elongated, adds processing cost；On the other hand, the use of highly basic and organic solvent can be to ring
Border and health constitute potential threat.In view of the secondary pollution that the inorganic acid such as hydrochloric acid, sulfuric acid and nitric acid may be caused to environment,
The friendly organic acid of use environment turns into the focus studied recently, and such as CN 103641175A are using Organic Apple acid dissolving mangaic acid
Lithium anode material, in order to improve the leaching rate of cobalt, these techniques would generally add hydrogen peroxide or sulfurous acid in step of acid dipping
The reducing agents such as sodium.However, these current recovery technologies it is main using reclaim the valuable metals such as cobalt and lithium in lithium ion battery as
Purpose, anode waste generally separates and recovers the metal in leachate using the precipitation method, solvent extraction, crystallisation after leaching, but
It is not carried out the closed loop cycle of metal component in anode waste.
In a word, the lithium ion cell anode waste based on metal closed loop cycle can also up to the present be realized without a kind of
Inexpensive short distance recovery technology, and for other chemical compositions anode waste and blended anode waste material recovery technology particularly
It is deficient.
The content of the invention
In view of the deficienciess of the prior art, an object of the present invention is to provide gold in lithium ion cell anode waste
Belong to the leaching method of ion, the second object of the present invention is to provide a kind of lithium ion cell positive based on metal closed loop cycle
The leaching rate of the leaching method metal of metal ion is high in the recovery method of waste material, the lithium ion cell anode waste, part
Organic acid recoverable, processing cost is low, and does not produce secondary pollution.
For up to this purpose, the present invention uses following technical scheme：
On the one hand, the invention provides a kind of leaching method of metal in lithium ion cell anode waste, methods described is：
Lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent, separation of solid and liquid is carried out after reaction, is obtained
Leachate and filter residue, realize the leaching of metal in lithium ion cell anode waste.
The lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent again after drying.
Preferably, the temperature of the drying is 60~200 DEG C, such as 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110, DEG C 130 DEG C,
150 DEG C, 170 DEG C, 180 DEG C or 190 DEG C etc., preferably 65 DEG C~130 DEG C；The dry time be 6~24h, such as 7h, 9h, 10h,
12h, 15h, 17h, 18h, 19h, 21h, 22h or 23h etc., preferably 12h~18h.
Preferably, the drying is convection drying or dried after broken.
Preferably, it is described to be broken for lithium ion cell anode waste being broken into the broken of 5mm~15mm × 5mm~15mm
Piece, such as 5mm × 10mm, 5mm × 5mm, 10mm × 15mm, 5mm × 15mm or 5mm × 12mm's, preferably 10mm × 10mm
Fragment, with the mass transfer of strengthening subsequent leaching process.
Active material in the lithium ion cell anode waste is LiFePO4, nickel-based oxide, cobalt base oxide or
Any of manganese-base oxide or at least two combination.
When anode waste active material include LiFePO4 when, Fe concentration can be caused of a relatively high, it is carried out from
Son doping makes it meet LiNi, it is necessary to add substantial amounts of Ni salt, Co salt or Mn salt to adjust the content of metalxCoyMn1-x-y- zMzO2In each metallic element mol ratio.
Preferably, the active material in the lithium ion cell anode waste is cobalt acid lithium (LiCoO2), lithium nickelate
(LiNiO2), LiMn2O4 (LiMnO2Or LiMn2O4), binary composite positive pole or one kind in ternary composite cathode material or
At least two combination.
The binary composite positive pole for positive electrode active component in addition to lithium, also containing other two kinds of gold
Category.
Preferably, the binary composite positive pole is LiNixCo1–xO2、LiNixMn1–xO2Or LiCo1–xMnxO2In one
Kind or at least two combination, wherein, 0<x<1, preferably x are 0.5.Typical but non-limiting combination has：LiNixCo1–xO2With
LiNixMn1–xO2Combination, LiNixMn1–xO2And LiCo1–xMnxO2Combination, LiNixCo1–xO2、LiNixMn1–xO2And LiCo1– xMnxO2Combination etc..
The ternary composite cathode material for positive electrode active component in addition to lithium, also containing other three kinds of gold
Category.
Preferably, the ternary composite cathode material is LiNixCoyMnl–x–yO2And/or LiNixCoyAll–x–yO2, wherein,
0<x<1,0<y<1, and 0<x+y<1.LiNixCoyMnl–x–yO2The middle typical mol ratio of Ni, Co and Mn is 1:1:1、5:2:3、4:2:
4、4:2:2、8:1:1 etc..
The recovery method scope of application for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided is wide,
The recycling of the anode waste and its mixture of phosphoric acid iron lithium, Ni-based, cobalt-based or manganese base can be applied to, be adapted to extensive
Handle lithium ion cell anode waste.
The solid-to-liquid ratio of the lithium ion cell anode waste and the organic acid soln containing reducing agent is 40~150gL-1,
Such as 50gL-1、60g·L-1、70g·L-1、90g·L-1、100g·L-1、110g·L-1、130g·L-1、140g·L-1Or
145g·L-1Deng preferably 50~100gL-1。
Preferably, the lithium ion cell anode waste and the temperature of the organic acid soln reaction containing reducing agent for 15~
90 DEG C, preferably such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 85 DEG C, 30~70 DEG C.
Preferably, the lithium ion cell anode waste and the time of the organic acid soln reaction containing reducing agent for 5~
40min, such as 6min, 7min, 10min, 12min, 15min, 20min, 25min, 30min or 35min, preferably 10~
30min。
Preferably, the lithium ion cell anode waste enters under agitation with the organic acid soln reaction containing reducing agent
OK, the speed of the stirring be 100~500rpm, such as 120rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm,
400rpm, 450rpm or 480rpm etc..
Preferably, the separation of solid and liquid can reach the purpose of separation solid and liquid, typical but non-limiting
Solid-liquid separation method is：Filtering or centrifugation etc..
Preferably, the concentration of organic acid is 1.0~7.0molL in the organic acid soln-1, such as 1.5molL-1、
2.0mol·L-1、2.5mol·L-1、3.0mol·L-1、3.5mol·L-1、4.0mol·L-1、4.5mol·L-1、5.0mol·
L-1、5.5mol·L-1、6.0mol·L-1Or 6.5molL-1Deng preferably 2.0~4.0molL-1。
Preferably, the organic acid be contain or not contain substituent carbon number be 1~5 organic carboxyl acid.
Preferably, the organic carboxyl acid is any of formic acid, acetic acid, propionic acid, butyric acid or valeric acid or at least two
Combination, it is typical but non-limiting to be combined as：The group of the combination of the combination of formic acid and acetic acid, propionic acid and butyric acid, valeric acid and formic acid
Close, the combination of acetic acid and butyric acid, formic acid, acetic acid, combination of propionic acid and butyric acid etc..
Preferably, the substituent is any of fluorine, chlorine, bromine or iodine or at least two, preferably fluorine and chlorine.
Preferably, the number of the substituent is 1~9, such as 2,3,4,5,6,7 or 8, preferably
For 3~6.
Preferably, in the organic acid soln reducing agent weight/mass percentage composition be 1~12%, such as 2%, 3%, 4%,
5%th, 6%, 7%, 8%, 9%, 10% or 11% etc., preferably 2~6%.
Preferably, the reducing agent is the material with reproducibility, such as sulfurous acid, sodium sulfite, sulphur in acid condition
Any of sodium thiosulfate or hydrogen peroxide or at least two combination, preferably hydrogen peroxide.
Preferably, the filter residue is reacted with the organic acid soln containing reducing agent again, fully to leach the filter
Metallic element in slag.
The leaching method of metal uses degradable organic acid soln in the lithium ion cell anode waste that the present invention is provided
The metal in lithium ion cell anode waste is dissolved, the leaching rate of metal is high, extraction time is short, the recyclable profit of part organic acid
With cost not only having been saved, while avoiding prior art uses the secondary pollution that is likely to result in environment of inorganic acid.
On the other hand, the invention provides a kind of recovery side of the lithium ion cell anode waste based on metal closed loop cycle
Method, the described method comprises the following steps：
(1) lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent, consolidated after reaction
Liquid is separated, and is obtained leachate and filter residue, is realized the leaching of metal in lithium ion cell anode waste；
(2) one kind in the element composition and content in leachate, regulation leachate in Ni, Co, Mn or M or at least
The content of two kinds of elements, makes Ni, Co, Mn and M mol ratio meet molecular formula LiNixCoyMn1-x-y-zMzO2Middle Ni, Co, Mn and M
Mol ratio, wherein, M is any of Cu, Al, Fe, Mg, Cr, Ti, Ce or Y or at least two, 0<x<1,0<y<1,0≤z
<0.1, and 0<x+y+z<1, obtain precursor solution；
(3) positive active material presoma is prepared using precursor solution, and obtains lithium-containing solution；
Optionally, step (4) is carried out：Reclaim the lithium in lithium-containing solution.
The molecular formula LiNixCoyMn1-x-y-zMzO2In, M be any of Cu, Al, Fe, Mg, Cr, Ti, Ce or Y or
At least two, such as M are Cu and Al, Fe and Mg, Cr and Ti, Ce and Y, Cu, Al and Fe, Cr, Ti, Ce and Y etc., and the M is derived from
Foreign metal that separation lithium ion cell anode waste obtains being mixed into during positive active material, positive active material are due to mixing
The water soluble salt of the introduced metal of miscellaneous or coating modification or M；0<x<1,0<y<1,0≤z<0.1, and 0<x+y+z<1, as x is
0.1st, 0.2,0.3,0.5,0.7,0.8 or 0.9 etc., y be 0.1,0.2,0.3,0.5,0.7,0.8 or 0.9 etc., z be 0,0.02,
0.05th, 0.07,0.08 or 0.09 etc., when not being mixed into any impurity in the separation process of lithium ion cell anode waste, and just
Pole active material is handled without ion doping or coating modification, i.e., Li, Ni, Co and Mn these four metals are comprised only in anode waste
When, z can think 0.
The recovery method for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided is without by pre-
Process step separates anode material for lithium-ion batteries and aluminum foil current collector, shortens technological process, reduces processing cost, simultaneously
That environmental and human health impacts are caused when avoiding prior art using strong base solution or organic solvent separation positive electrode is potential
Secondary pollution risk.
Step (1) lithium ion cell anode waste carries out anti-with the organic acid soln containing reducing agent again after drying
Should.
Preferably, the temperature of the drying is 60~200 DEG C, such as 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110, DEG C 130 DEG C,
150 DEG C, 170 DEG C, 180 DEG C or 190 DEG C etc., preferably 65 DEG C~130 DEG C；The dry time be 6~24h, such as 7h, 9h, 10h,
12h, 15h, 17h, 18h, 19h, 21h, 22h or 23h etc., preferably 12h~18h.
Preferably, the drying is convection drying or dried after broken.
Preferably, it is described to be broken for lithium ion cell anode waste being broken into the broken of 5mm~15mm × 5mm~15mm
Piece, such as 5mm × 10mm, 5mm × 5mm, 10mm × 15mm, 5mm × 15mm or 5mm × 12mm's, preferably 10mm × 10mm
Fragment, with the mass transfer of strengthening subsequent leaching process.
Active material in step (1) described lithium ion cell anode waste is LiFePO4, nickel-based oxide, cobalt-based oxygen
Any of compound or manganese-base oxide or at least two combination.
When anode waste active material include LiFePO4 when, Fe concentration can be caused of a relatively high, it is carried out from
Son doping makes it meet LiNi, it is necessary to add substantial amounts of Ni salt, Co salt or Mn salt to adjust the content of metalxCoyMn1-x-y- zMzO2In each metallic element mol ratio.
Preferably, the active material in step (1) described lithium ion cell anode waste is cobalt acid lithium (LiCoO2), nickel acid
Lithium (LiNiO2), LiMn2O4 (LiMnO2Or LiMn2O4), one kind in binary composite positive pole or ternary composite cathode material
Or at least two combination.
The binary composite positive pole for positive electrode active component in addition to lithium, also containing other two kinds of gold
Category.
Preferably, the binary composite positive pole is LiNixCo1–xO2、LiNixMn1–xO2Or LiCo1–xMnxO2In one
Kind or at least two combination, wherein, 0<x<1, preferably x are 0.5.Typical but non-limiting combination has：LiNixCo1–xO2With
LiNixMn1–xO2Combination, LiNixMn1–xO2And LiCo1–xMnxO2Combination, LiNixCo1–xO2、LiNixMn1–xO2And LiCo1– xMnxO2Combination etc..
The ternary composite cathode material for positive electrode active component in addition to lithium, also containing other three kinds of gold
Category.
Preferably, the ternary composite cathode material is LiNixCoyMnl–x–yO2And/or LiNixCoyAll–x–yO2, wherein,
0<x<1,0<y<1, and 0<x+y<1.LiNixCoyMnl–x–yO2The middle typical mol ratio of Ni, Co and Mn is 1:1:1、5:2:3、4:2:
4、4:2:2、8:1:1 etc..
The recovery method scope of application for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided is wide,
The recycling of the anode waste and its mixture of phosphoric acid iron lithium, Ni-based, cobalt-based or manganese base can be applied to, be adapted to extensive
Handle lithium ion cell anode waste.
The solid-to-liquid ratio of step (1) lithium ion cell anode waste and the organic acid soln containing reducing agent for 40~
150g·L-1, such as 50gL-1、60g·L-1、70g·L-1、90g·L-1、100g·L-1、110g·L-1、130g·L-1、
140g·L-1Or 145gL-1Deng preferably 50~100gL-1。
Preferably, step (1) lithium ion cell anode waste and the temperature of the organic acid soln reaction containing reducing agent
Spend for 15~90 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C or 85 DEG C, preferably 30~70 DEG C.
Preferably, step (1) lithium ion cell anode waste with containing reducing agent organic acid soln reaction when
Between be 5~40min, such as 6min, 7min, 10min, 12min, 15min, 20min, 25min, 30min or 35min, be preferably
10~30min.
Preferably, step (1) lithium ion cell anode waste is being stirred with the organic acid soln reaction containing reducing agent
Mix lower progress, the speed of the stirring is 100~500rpm, such as 120rpm, 150rpm, 200rpm, 250rpm, 300rpm,
350rpm, 400rpm, 450rpm or 480rpm etc..
Preferably, step (1) described separation of solid and liquid can reach the purpose of separation solid and liquid, typical but non-limit
The solid-liquid separation method of property processed is：Filtering or centrifugation etc..
Preferably, the concentration of organic acid is 1.0~7.0molL in step (1) described organic acid soln-1, such as
1.5mol·L-1、2.0mol·L-1、2.5mol·L-1、3.0mol·L-1、3.5mol·L-1、4.0mol·L-1、4.5mol·
L-1、5.0mol·L-1、5.5mol·L-1、6.0mol·L-1Or 6.5molL-1Deng preferably 2.0~4.0molL-1。
Preferably, step (1) described organic acid be contain or not contain substituent carbon number be 1~5 organic carboxylic
Acid.
Preferably, step (1) described organic carboxyl acid is any of formic acid, acetic acid, propionic acid, butyric acid or valeric acid or at least
Two kinds of combination, it is typical but non-limiting to be combined as：The combination of the combination of formic acid and acetic acid, propionic acid and butyric acid, valeric acid and first
The combination of acid, the combination of acetic acid and butyric acid, formic acid, acetic acid, combination of propionic acid and butyric acid etc..
Preferably, the substituent is any of fluorine, chlorine, bromine or iodine or at least two, preferably fluorine and chlorine.
Preferably, the number of the substituent is 1~9, such as 2,3,4,5,6,7 or 8, preferably
For 3~6.
Preferably, the weight/mass percentage composition of reducing agent is 1~12% in step (1) described organic acid soln, such as 2%,
3%th, 4%, 5%, 6%, 7%, 8%, 9%, 10% or 11% etc., preferably 2~6%.
Preferably, step (1) described reducing agent is the material with reproducibility, such as sulfurous acid, sulfurous in acid condition
Any of sour sodium, sodium thiosulfate or hydrogen peroxide or at least two combination, preferably hydrogen peroxide.
Preferably, step (1) described filter residue is reacted with the organic acid soln containing reducing agent again, fully to leach
Metallic element in the filter residue.
The leaching method of metal uses degradable organic acid soln in the lithium ion cell anode waste that the present invention is provided
The metal in lithium ion cell anode waste is dissolved, the leaching rate of metal is high, extraction time is short, the recyclable profit of part organic acid
With cost not only having been saved, while avoiding prior art uses the secondary pollution that is likely to result in environment of inorganic acid.
The leaching method of metal can be with the utilization of follow-up leachate in the lithium ion cell anode waste that the present invention is provided
To be oriented to, by regulating and controlling the foreign metal ion content in leaching process control leachate：If being synthesized using obtained leachate
Nickel-cobalt-manganese ternary presoma, then require that the content of foreign metal ion in leachate is as far as possible low；If synthesizing metal using leachate
The nickel-cobalt-manganese ternary presoma of ion doping, then can pass through according to the molecular formula of the positive active material presoma being fitted to
Adjust the content of foreign metal ion in organic acid and the concentration of reducing agent and the time of leaching and temperature control leachate, it is to avoid
The Complicated Flow of separating-purifying is carried out to various metals in leachate in the prior art, lithium ion cell anode waste is realized
The leaching of middle whole metals.
The content of one kind or at least two elements in step (2) the regulation leachate in Ni, Co, Mn or M is to institute
State one kind in the water soluble salt that the water soluble salt of nickel, the water soluble salt of cobalt, the water soluble salt of manganese or M are added in leachate or extremely
Few two kinds composition.
Preferably, the moon in the water soluble salt of the nickel, the water soluble salt of cobalt, the water soluble salt of manganese or M water soluble salt
Ion independently is any of chlorion, sulfate ion, nitrate ion, acetate ion or oxalate denominationby or extremely
It is few two kinds.
As preferred technical scheme, the step (2) is specially：
A：Measure the element composition and constituent content of leachate；
B：According to step A measurement result and molecular formula LiNixCoyMn1-x-y-zMzO2, regulation leachate in nickel, cobalt, manganese or
The content of one kind or at least two elements in M, obtains precursor solution.
The measuring method of the step A can be：The leachate is diluted, with ICP-OES determine solution in nickel, cobalt, manganese,
The concentration of lithium and M.
The preparation method of step (3) the positive active material presoma is coprecipitation.Concretely comprise the following steps：To before described
Drive in liquid solution and add alkali lye so that coprecipitation reaction, then solid-liquid point occur for the metal ion in precursor solution in addition to lithium
From obtaining positive active material presoma and lithium-containing solution.The alkali lye be sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor,
One kind or at least two mixture in sodium carbonate liquor, solution of potassium carbonate or sal volatile.The separation of solid and liquid can
The purpose of precipitation and separation and solution is reached, can be filtering or centrifugation etc..
Preferably, the lithium in step (4) the recovery lithium-containing solution is：Into lithium-containing solution add water soluble carbonate,
One kind or at least two mixture in water-soluble phosphate or soluble fluoride, and carry out separation of solid and liquid.
Preferably, the cation in the water soluble carbonate, water-soluble phosphate or soluble fluoride independently is
One kind or at least two combination in sodium, potassium or ammonium ion.
The recovery method also includes step (5)：The positive pole that obtained lithium is obtained with step (3) is reclaimed using step (4)
Active material presoma prepares active substance of lithium ion battery anode.
The positive active material is prepared by high temperature solid state reaction.The high temperature solid state reaction refers in high temperature
Under (800~900 DEG C), by contact, reaction, nucleation and crystal growth between solid interface, and composite oxides, oxyacid are generated
Salt, binary or polynary ceramic compound etc..
Preferably, the temperature of the high temperature solid state reaction is 800~900 DEG C, such as 800 DEG C, 820 DEG C, 850 DEG C or 870 DEG C
Deng.
Compared with prior art, beneficial effects of the present invention are：
(1) in the lithium ion cell anode waste that provides of the present invention metal leaching method, the leaching rate of metal is high, leach
Time is short, part organic acid recoverable, has not only saved cost, while avoiding prior art using inorganic acid to environment
The secondary pollution being likely to result in；
(2) the recovery method scope of application for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided
Extensively, it can be used in the recycling of phosphoric acid iron lithium, Ni-based, cobalt-based, manganese-based anode waste material and its mixture, it is adaptable to extensive
Handle lithium ion cell anode waste；
(3) recovery method for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided need not pass through
Pre-treatment step separates anode material for lithium-ion batteries and aluminum foil current collector, shortens technological process, reduces processing cost, together
When environmental and human health impacts are caused when avoiding prior art using strong base solution or organic solvent separation positive electrode it is latent
In secondary pollution risk；
(4) recovery method for the lithium ion cell anode waste based on metal closed loop cycle that the present invention is provided passes through regulation and control
Foreign metal ion content in leaching process control leachate, with follow-up leachate be utilized as be oriented to, it is to avoid existing skill
The Complicated Flow of separating-purifying is carried out in art to various metals in leachate, the closed loop cycle for realizing metal is utilized.
Brief description of the drawings
Time for the lithium ion cell anode waste based on metal closed loop cycle that Fig. 1 provides for one embodiment of the present invention
Receive process chart；
Fig. 2 is that (wherein illustration is anti-for the leaching rate of nickel in leachate under the differential responses time in embodiment 1, cobalt, manganese and lithium
It is the leaching rate of the metal under the conditions of 5min~30min between seasonable)；
Fig. 3 be in embodiment 1 under the differential responses time in leachate aluminium leaching rate；
Fig. 4 is that (wherein illustration is anti-for the leaching rate of nickel in leachate under the differential responses time in embodiment 2, cobalt, manganese and lithium
It is the leaching rate of the metal under the conditions of 2min~15min between seasonable)；
Fig. 5 be in embodiment 2 under the differential responses time in leachate aluminium leaching rate；
Fig. 6 is the leaching rate of nickel in leachate under different content of hydrogen peroxide in comparative example 1, cobalt, manganese, lithium and aluminium；
Fig. 7 is the leaching rate of nickel in leachate under different acetic acid concentrations in comparative example 2, cobalt, manganese, lithium and aluminium.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.The skill of this area
Understanding is of the invention it will be clearly understood that the embodiment is only to aid in by art personnel, is not construed as the concrete restriction to the present invention.
Fig. 1 is returning for the lithium ion cell anode waste based on metal closed loop cycle that one embodiment of the present invention is provided
The process chart of receiving method, the recovery method is：
(1) it will be dried after nickel, cobalt, manganese base lithium ion cell anode waste coarse crushing；
(2) dried lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent, reacted
Filtered afterwards, obtain leachate and filter residue, realize the leaching of metal ion in lithium ion cell anode waste, the filter residue weight
Newly reacted with the organic acid soln containing reducing agent；
(3) the element composition and content in leachate, the one kind added into leachate in nickel salt, cobalt salt or manganese salt
Or at least two, to adjust one kind in leachate in Ni, Co or Mn or the content of at least two elements, make Ni, Co and Mn
Mol ratio meets molecular formula LiNixCoyMn1-x-y-zMzO2Middle Ni, Co, Mn and M mol ratio, obtain precursor solution；
(4) positive active material forerunner is prepared by the coprecipitation of industrial comparative maturity using precursor solution
Body, and obtain lithium-containing solution；
(5) lithium in lithium-containing solution is reclaimed.
Embodiment 1
The recovery method of lithium ion cell anode waste based on metal closed loop cycle is comprised the following steps that：
(1) the anode waste 30g produced in ternary composite cathode material of lithium ion battery nickle cobalt lithium manganate production process is taken,
About 10mm × 10mm anode waste fragment is cut into first, and these fragments are then placed in freeze-day with constant temperature in 65 DEG C of drying boxes
24h, and the composition of the metallic element in dried anode waste and content are measured, as a result as shown in table 1.
The weight/mass percentage composition of metal in the dried nickle cobalt lithium manganate anode waste of table 1
| Metal | Ni | Co | Mn | Li | Al |
| Mass content (wt.%) | 18.32 | 18.65 | 17.57 | 6.15 | 7.86 |
(2) the dried anode waste fragment obtained by step (1) that 9 parts of quality are about 2.5g is taken respectively, is added respectively
In the conical flask for entering to 9 to fill 50mL trichloroacetic acids and hydrogen peroxide (30wt.%) mixed aqueous solution, 1-9 is respectively labeled as
Number.The concentration of trichloroacetic acid is 3.0molL in the 1-9 conical flasks-1, the weight/mass percentage composition of hydrogen peroxide is
4wt.%.The 1-9 conical flasks are placed in shaking bath and reacted, controlling reaction temperature is 60 DEG C, stir speed (S.S.) is
230rpm, the reaction time is as shown in table 2.
After conical flask reaches the default reaction time, taken out successively from shaking bath and fast filtering is to realize solid-liquid
Separation, is repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made is collected after conical flask 3 times, after filtering respectively
10 times and 100 times of dilution, determines nickel, cobalt, manganese, lithium and aluminum ions concentration in solution with ICP-OES, is obtained according to step (1)
Dried anode waste fragment in above-mentioned metal content, calculate the leaching rate of above-mentioned metal.The filter residue obtained after filtering
Again reacted with the organic acid containing reducing agent.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate are shown in the leachate that the differential responses time obtains under the conditions of the present embodiment
Table 2, Fig. 2 and Fig. 3.
The leaching rate of metal in the leachate that the differential responses time of table 2 obtains
From table 2, Fig. 2 and Fig. 3, under the conditions of the present embodiment, when reacted between be 30min when, obtained leachate
The leaching rate of middle aluminium is only 7.04%, and nickel, cobalt, the leaching rate of manganese and lithium are then up to 92.99%, 91.80%, 89.78% and
99.67%, that is, effective control of aluminium ion leaching rate in realizing while nickel, cobalt, manganese and lithium high leaching rate to leachate.
(3) according to the molecular formula Ni of aluminium doping nickel cobalt manganese presoma to be synthesized1/3Mn1/3Co1/3–1/20Al1/20(OH)2Or
Ni1/3Mn1/3Co1/3–1/20Al1/20CO3, by adding the component of nickel nitrate, cobalt nitrate or manganese nitrate to leachate into leachate
Regulated and controled, obtain nickel cobalt manganese precursor solution.
(4) by the Co deposited synthesis nickel cobalt manganese presoma of industrial comparative maturity, and lithium-containing solution is obtained.
(5) saturated sodium carbonate solution is added into lithium-containing solution, makes Li therein+With Li2CO3Form reclaim, realize
The closed loop cycle of metal is utilized in nickle cobalt lithium manganate anode waste.
Embodiment 2
The recovery method of lithium ion cell anode waste based on metal closed loop cycle is comprised the following steps that：
(1) cobalt acid lithium (LiCoO separated from lithium ion battery is taken respectively2) anode waste 10g and nickel ion doped
(LiNi1/2Mn1/2O2) anode waste 20g, their size is about 5mm~15mm × 5mm~15mm, and they are well mixed simultaneously
The freeze-day with constant temperature 12h in 130 DEG C of drying boxes, obtains dried blended anode waste material, measures dried blended anode waste material
The component and content of middle metallic element, as a result as shown in table 3.
The weight/mass percentage composition of the dried blended anode metals from waste of table 3
| Metal | Ni | Co | Mn | Li | Al |
| Mass content (wt.%) | 19.21 | 17.83 | 18.92 | 6.95 | 10.71 |
(2) the dried blended anode waste material obtained by step (1) that 9 parts of quality are about 2.5g is taken respectively, is added respectively
In the conical flask for entering to 9 to fill 50mL trichloroacetic acids and hydrogen peroxide (30wt.%) mixed aqueous solution, 1-9 is respectively labeled as
Number.The concentration of trichloroacetic acid is 3.0molL in the 1-9 conical flasks-1, the weight/mass percentage composition of hydrogen peroxide is
6wt.%.The 1-9 conical flasks are placed in water-bath and reacted, controlling reaction temperature is 70 DEG C, and stir speed (S.S.) is 300rpm,
Reaction time is as shown in table 3.
After conical flask reaches the default reaction time, taken out successively from shaking bath and fast filtering is to realize solid-liquid
Separation, is repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made is collected after conical flask 3 times, after filtering respectively
10 times and 100 times of dilution, determines nickel, cobalt, manganese, lithium and aluminum ions concentration in solution with ICP-OES, is obtained according to step (1)
Dried anode waste fragment in above-mentioned metal content, calculate the leaching rate of above-mentioned metal.The filter residue obtained after filtering
Again reacted with the organic acid containing reducing agent.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate are shown in the leachate that the differential responses time obtains under the conditions of the present embodiment
Table 4, Fig. 4 and Fig. 5.
The leaching rate of metal in the leachate that the differential responses time of table 4 obtains
From table 4, Fig. 4 and Fig. 5, under the conditions of the present embodiment, when reacted between be 15min when, obtained leachate
The leaching rate of middle aluminium is only 7.46%, and nickel, cobalt, the leaching rate of manganese and lithium are then up to 93.95%, 91.56%, 91.84% and
99.61%, that is, effective control of aluminium ion leaching rate in realizing while nickel, cobalt, manganese and lithium high leaching rate to leachate.
(3) (4) (5) in step (3) (4) (5) be the same as Example 1.
Embodiment 3
The recovery method of lithium ion cell anode waste based on metal closed loop cycle is comprised the following steps that：
(1) take respectively and nickle cobalt lithium manganate (LiNi is separated from lithium ion batteryxCoyMnl–x–yO2) anode waste 30g,
Size is about 10mm × 15mm, the freeze-day with constant temperature 6h in 200 DEG C of drying boxes, obtains dried blended anode waste material, and measurement is dry
The component and content of blended anode metals from waste after dry, as a result as shown in table 5.
The weight/mass percentage composition of the dried blended anode metals from waste of table 5
| Metal | Ni | Co | Mn | Li | Al |
| Mass content (wt.%) | 20.13 | 18.79 | 19.25 | 7.03 | 8.22 |
(2) the dried anode waste obtained by step (1) for taking quality to be about 2.0g, is added to and fills 50mL formic acid
In the conical flask of sodium sulfite mixed aqueous solution.The concentration of the formic acid is 1.0molL-1, the quality percentage of sodium sulfite
Content is 12wt.%.The conical flask is placed in water-bath and reacted, controlling reaction temperature is 15 DEG C, stir speed (S.S.) is
500rpm, the reaction time is 40min.
After conical flask reaches the default reaction time, taken out from shaking bath and fast filtering is to realize solid-liquid point
From, repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made are collected after conical flask 3 times, it is dilute respectively after filtering
10 times and 100 times are released, nickel, cobalt, manganese, lithium and aluminum ions concentration in solution is determined with ICP-OES, is obtained according to step (1)
The content of above-mentioned metal in dried anode waste fragment, calculates the leaching rate of above-mentioned metal.The filter residue weight obtained after filtering
Newly reacted with the organic acid containing reducing agent.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate are shown in Table 6 in the leachate obtained under the conditions of the present embodiment.
The leaching rate of metal in the leachate of table 6
| Metal | Nickel | Cobalt | Manganese | Lithium | Aluminium |
| Leaching rate (wt.%) | 94.25 | 93.91 | 95.64 | 98.89 | 14.34 |
As shown in Table 6, under the conditions of the present embodiment, the leaching rate of aluminium is only 14.34% in obtained leachate, and nickel,
The leaching rate of cobalt, manganese and lithium then be up to 94.25%, 93.91%, 95.64% and 98.89%, that is, realize nickel, cobalt, manganese and
Effective control while lithium high leaching rate to aluminium ion leaching rate in leachate.
(3) according to the molecular formula Ni of aluminium doping nickel cobalt manganese presoma to be synthesized1/3Mn1/3Co1/3–1/15Al1/15(OH)2Or
Ni1/3Mn1/3Co1/3–1/15Al1/15CO3, by adding the component of nickel nitrate, cobalt nitrate or manganese nitrate to leachate into leachate
Regulated and controled, obtain nickel cobalt manganese precursor solution.
(4) by the Co deposited synthesis nickel cobalt manganese presoma of industrial comparative maturity, and lithium-containing solution is obtained.
(5) unsaturated carbonate ammonium salt solution is added into lithium-containing solution, makes Li therein+With Li2CO3Form reclaim, realize
The closed loop cycle of metal is utilized in nickle cobalt lithium manganate anode waste.
Embodiment 4
The recovery method of lithium ion cell anode waste based on metal closed loop cycle is comprised the following steps that：
(1) nickel ion doped (LiNi separated from lithium ion battery is taken respectively1/2Mn1/2O2) anode waste 30g, it
Size be about 15mm × 15mm, by their well mixed and freeze-day with constant temperature 12h in 60 DEG C of drying boxes, obtain dried
Blended anode waste material, measures the component and content of dried blended anode metals from waste, as a result as shown in table 7.
The weight/mass percentage composition of the dried blended anode metals from waste of table 7
| Metal | Ni | Mn | Li | Al |
| Mass content (wt.%) | 17.93 | 16.27 | 5.99 | 7.21 |
(2) the dried blended anode waste material obtained by step (1) for taking quality to be about 7.5g, is added separately to fill
In the conical flask of 50mL fluorine valeric acid and sodium sulfite mixed aqueous solution.The concentration of fluorine valeric acid is 7.0molL in the conical flask-1, the weight/mass percentage composition of sodium sulfite is 1wt.%.The conical flask is placed in water-bath and reacted, controlling reaction temperature is
90 DEG C, stir speed (S.S.) is 100rpm, and the reaction time is 5min.
After conical flask reaches the default reaction time, taken out from shaking bath and fast filtering is to realize solid-liquid point
From, repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made are collected after conical flask 3 times, it is dilute respectively after filtering
10 times and 100 times are released, nickel, manganese, lithium and aluminum ions concentration, the drying obtained according to step (1) in solution are determined with ICP-OES
The content of above-mentioned metal in anode waste fragment afterwards, calculates the leaching rate of above-mentioned metal.The filter residue obtained after filtering again with
Organic acid containing reducing agent is reacted.
Nickel, manganese, lithium and aluminum ions leaching rate are shown in Table 8 in the leachate obtained under the conditions of the present embodiment.
The leaching rate of metal in the leachate of table 8
| Metal | Nickel | Manganese | Lithium | Aluminium |
| Leaching rate (wt.%) | 70.39 | 69.84 | 85.56 | 1.87 |
As shown in Table 8, under the conditions of the present embodiment, the leaching rate of aluminium is only 1.87% in obtained leachate, and nickel, manganese
Leaching rate with lithium is respectively then 70.39%, 69.84% and 85.56%, that is, is realized in nickel, manganese and the higher leaching rate of lithium
Effective control to aluminium ion leaching rate in leachate simultaneously.
(3) according to the molecular formula Ni of aluminium doping nickel manganese presoma to be synthesized1/2Mn1/2–1/20Al1/20(OH)2Or Ni1/ 2Mn1/2–1/20Al1/20CO3, the component of leachate is regulated and controled by adding nickel nitrate or manganese nitrate into leachate, nickel is obtained
Manganese precursor solution.
(4) aluminium doping nickel manganese presoma is prepared by the coprecipitation of industrial comparative maturity, and obtains lithium-containing solution.
(5) unsaturated carbonate potassium solution is added into lithium-containing solution, makes Li therein+With Li2CO3Form reclaim, realize
The closed loop cycle of metal is utilized in nickle cobalt lithium manganate anode waste.
(6) obtained Li will be reclaimed using high temperature solid state reaction2CO3In temperature it is 800 with the nickel manganese presoma for preparing
Under the conditions of DEG C, LiNi is prepared1/2Mn1/2–1/20Al1/20O2。
Comparative example 1
The recovery method of lithium ion cell anode waste is comprised the following steps that：
Step (1) be the same as Example 1, remaining step is as follows：
(2) the dried anode waste fragment obtained by step (1) that 7 parts of quality are about 2.5g is taken respectively, is added respectively
In the conical flask for entering to 7 to fill 50mL trichloroacetic acids and hydrogen peroxide (30wt.%) mixed aqueous solution, labeled as No. 1-7.Institute
The concentration for stating trichloroacetic acid in 1-7 conical flasks is 3.0molL–1, quality percentage of the hydrogen peroxide in mixed aqueous solution
Content is as shown in table 9.The 1-7 conical flasks are placed in shaking bath and reacted, controlling reaction temperature is 60 DEG C, reaction time
For 240min, stir speed (S.S.) is 230rpm.
After conical flask reaches the default reaction time, taken out successively from shaking bath and fast filtering is to realize solid-liquid
Separation, is repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made is collected after conical flask 3 times, after filtering respectively
10 times and 100 times of dilution, determines nickel, cobalt, manganese, lithium and aluminum ions concentration in solution with ICP-OES, is obtained according to step (1)
Dried anode waste fragment in above-mentioned metal content, calculate the leaching rate of above-mentioned metal.The filter residue obtained after filtering
Again reacted with the organic acid containing reducing agent.
Nickel, cobalt, manganese, lithium and aluminum ions leaching in the leachate that different content of hydrogen peroxide are obtained under the conditions of this comparative example
Rate is shown in Table 9 and Fig. 6.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate in the leachate that the different content of hydrogen peroxide of table 9 are obtained
From table 9 and Fig. 6, under the conditions of this comparative example, even if the reaction time 240min will be extended to, when without mistake
During hydrogen oxide reducing agent, nickel in obtained leachate, cobalt, the leaching rate of manganese and lithium are respectively 53.01%, 51.39%,
52.13% and 84.07%, it can not now realize the high efficiente callback of above-mentioned 4 kinds of metals.When content of hydrogen peroxide is 4wt.%,
Nickel in obtained leachate, cobalt, the leaching rate of manganese and lithium then respectively reach 94.17%, 91.41%, 91.11% and 99.58%,
Therefore the presence of appropriate reducing agent can effectively improve the leaching rate of above-mentioned metal.Further increase reducing agent consumption improves processing
Cost, but metal leaching rate has no and significantly improves, and is 2~6wt.% it is advantageous to the consumption of reducing agent.By further controlling
Reaction time just can effectively control the leaching rate of aluminium in leachate, such as embodiment 1.When to sum up, to reduction agent content and reaction
Between control be the present invention key point.
Comparative example 2
The recovery method of lithium ion cell anode waste is comprised the following steps that：
(1) it is 1 in mass ratio:2:1 takes the cobalt acid lithium (LiCoO produced in lithium ion battery production process respectively2), nickel manganese
Sour lithium (LiNi1/2Mn1/2O2) and nickle cobalt lithium manganate (LiNi1/3Co1/3Mn1/3O2) anode waste 80g, first by these anode wastes
Coarse crushing into about 10mm × 10mm blended anode pieces of waste material and be sufficiently mixed uniform, they are then placed in 100 DEG C of Muffles
12h is dried in stove, dry blended anode pieces of waste material is obtained, the composition of the metal in dry blended anode waste material is measured and contains
Amount, as shown in table 10.
The weight/mass percentage composition of the dried blended anode metals from waste of table 10
| Metal | Ni | Co | Mn | Li | Al |
| Mass content (wt.%) | 20.15 | 17.41 | 19.73 | 7.34 | 10.02 |
(2) the dried blended anode pieces of waste material that the step of 9 parts of quality are about 5.0g (1) obtains is taken respectively, respectively
It is added in 9 conical flasks for filling 50mL acetic acid aqueous solutions, is respectively labeled as acetic acid in No. 1-9, the 1-9 conical flasks
Concentration is 1.0molL-1~5.0molL-1, it is specific as shown in table 11.The 1-9 conical flasks are placed in shaking bath
Reaction, controlling reaction temperature is 60 DEG C, and the reaction time is 240min, and stir speed (S.S.) is 230rpm.
After conical flask reaches the default reaction time, taken out successively from shaking bath and fast filtering is to realize solid-liquid
Separation, is repeatedly washed with high purity water and leachate and cleaning solution and the solution that 1L is made is collected after conical flask 3 times, after filtering respectively
10 times and 100 times of dilution, determines nickel, cobalt, manganese, lithium and aluminum ions concentration in solution with ICP-OES, is obtained according to step (1)
Dried anode waste fragment in above-mentioned metal content, calculate the leaching rate of above-mentioned metal.The filter residue obtained after filtering
Again reacted with the organic acid containing reducing agent.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate are shown in the leachate that different acetic acid concentrations are obtained under the conditions of this comparative example
Table 11 and Fig. 7.
Nickel, cobalt, manganese, lithium and aluminum ions leaching rate in the leachate that the different acetic acid concentrations of table 11 are obtained
From table 11 and Fig. 7, under the conditions of the present embodiment, although the leaching rate of aluminium is respectively less than 10%, but does not have but
Obtain the high leaching rate of nickel, cobalt, manganese and lithium.When the concentration of acetic acid is 2.0molL-1When, nickel, cobalt, the leaching rate of manganese and lithium reach
To maximum, respectively 40.91%, 39.46%, 39.34% and 50.53%, but its leaching rate is far smaller than 90%, it is impossible to real
The complete leaching of metal in existing lithium ion cell anode waste, therefore the purpose of the present invention can not be realized (lithium ion cell positive gives up
The closed loop cycle of metal in material).
From above-described embodiment and comparative example, by (including species, the concentration of leaching agent and reducing agent to reaction system
With solid-to-liquid ratio etc.) and leaching process (including reaction temperature, time and stir speed (S.S.) etc.) regulation and control, it is possible to achieve nickel, cobalt, manganese and
Lithium height effectively controls the leaching rate of aluminium in leachate while leaching, and then realizes the purpose of the present invention.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (54)
1. the leaching method of metal in a kind of lithium ion cell anode waste, it is characterised in that methods described is：By lithium-ion electric
Pond anode waste is reacted with the organic acid soln containing reducing agent, and separation of solid and liquid is carried out after reaction, leachate and filter is obtained
Slag, realizes the leaching of metal in lithium ion cell anode waste；
The organic acid be contain or not contain substituent carbon number be 1~5 organic carboxyl acid, the substituent be fluorine,
Any of chlorine, bromine or iodine or at least two；
The reducing agent is any of sulfurous acid, sodium sulfite, sodium thiosulfate or hydrogen peroxide or at least two group
Close；
The temperature of the reaction is 15~90 DEG C, and the time of reaction is organic acid in 5~40min, described organic acid soln
Concentration is 1.0~7.0molL-1, the weight/mass percentage composition of reducing agent is 1~12% in organic acid soln；The lithium-ion electric
The solid-to-liquid ratio of pond anode waste and the organic acid soln containing reducing agent is 40~150gL-1。
2. leaching method according to claim 1, it is characterised in that the lithium ion cell anode waste dry after again with
Organic acid soln containing reducing agent is reacted.
3. leaching method according to claim 2, it is characterised in that the temperature of the drying is 60~200 DEG C, is dried
Time is 6~24h.
4. leaching method according to claim 2, it is characterised in that the drying is convection drying or dried after broken.
5. leaching method according to claim 4, it is characterised in that described to be broken for breaking lithium ion cell anode waste
It is broken into 5mm~15mm × 5mm~15mm fragment.
6. leaching method according to claim 4, it is characterised in that described to be broken for breaking lithium ion cell anode waste
It is broken into 10mm × 10mm fragment.
7. according to the method described in claim 1, it is characterised in that the active material in the lithium ion cell anode waste is
Any of LiFePO4, nickel-based oxide, cobalt base oxide or manganese-base oxide or at least two combination.
8. leaching method according to claim 1, it is characterised in that the active matter in the lithium ion cell anode waste
Matter is cobalt acid lithium, lithium nickelate, LiMn2O4, binary composite positive pole or one kind in ternary composite cathode material or at least two
Combination.
9. leaching method according to claim 8, it is characterised in that the binary composite positive pole is LiNixCo1– xO2、LiNixMn1–xO2Or LiCo1–xMnxO2In one kind or at least two combination, wherein, 0<x<1.
10. leaching method according to claim 8, it is characterised in that the ternary composite cathode material is
LiNixCoyMnl–x–yO2And/or LiNixCoyAll–x–yO2, wherein, 0<x<1,0<y<1, and 0<x+y<1.
11. leaching method according to claim 1, it is characterised in that the lithium ion cell anode waste is with containing also
The solid-to-liquid ratio of the organic acid soln of former agent is 50~100gL-1。
12. leaching method according to claim 1, it is characterised in that the lithium ion cell anode waste is with containing also
The temperature of the organic acid soln reaction of former agent is 30~70 DEG C.
13. leaching method according to claim 1, it is characterised in that the lithium ion cell anode waste is with containing also
The time of the organic acid soln reaction of former agent is 10~30min.
14. leaching method according to claim 1, it is characterised in that the lithium ion cell anode waste is with containing also
The reaction of the organic acid soln of former agent is carried out under agitation, and mixing speed is 100~500rpm.
15. leaching method according to claim 1, it is characterised in that the concentration of organic acid in described organic acid soln
For 2.0~4.0molL-1。
16. leaching method according to claim 1, it is characterised in that the quality hundred of reducing agent in the organic acid soln
It is 2~6% to divide content.
17. leaching method according to claim 1, it is characterised in that the separation of solid and liquid is filtering or centrifuges.
18. according to the method described in claim 1, it is characterised in that the organic carboxyl acid be formic acid, acetic acid, propionic acid, butyric acid or
Any of valeric acid or at least two combination.
19. leaching method according to claim 1, it is characterised in that the substituent is fluorine and chlorine.
20. leaching method according to claim 1, it is characterised in that the number of the substituent is 1~9.
21. leaching method according to claim 1, it is characterised in that the number of the substituent is 3~6.
22. leaching method according to claim 1, it is characterised in that the reducing agent is hydrogen peroxide.
23. leaching method according to claim 1, it is characterised in that the filter residue is again with containing the organic of reducing agent
Acid solution is reacted.
24. a kind of recovery method of the lithium ion cell anode waste based on metal closed loop cycle, it is characterised in that methods described
Comprise the following steps：
(1) lithium ion cell anode waste is reacted with the organic acid soln containing reducing agent, solid-liquid point is carried out after reaction
From obtaining leachate and filter residue, realize the leaching of metal ion in lithium ion cell anode waste；The organic acid be containing or
The carbon number for not containing substituent is 1~5 organic carboxyl acid, and the substituent is for any of fluorine, chlorine, bromine or iodine or extremely
It is few two kinds；The reducing agent is any of sulfurous acid, sodium sulfite, sodium thiosulfate or hydrogen peroxide or at least two
Combination；The temperature of the reaction is 15~90 DEG C, and the time of reaction is organic acid in 5~40min, described organic acid soln
Concentration is 1.0~7.0molL-1, the weight/mass percentage composition of reducing agent is 1~12%, the lithium-ion electric in organic acid soln
The solid-to-liquid ratio of pond anode waste and the organic acid soln containing reducing agent is 40~150gL-1；
(2) one kind or at least two in the element composition and content in leachate, regulation leachate in Ni, Co, Mn or M
The content of element, makes Ni, Co, Mn and M mol ratio meet molecular formula LiNixCoyMn1-x-y-zMzO2Middle Ni, Co, Mn and M's rubs
You compare, wherein, M is any of Cu, Al, Fe, Mg, Cr, Ti, Ce or Y or at least two, 0<x<1,0<y<1,0≤z<
0.1, and 0<x+y+z<1, obtain precursor solution；
(3) positive active material presoma is prepared using precursor solution, and obtains lithium-containing solution；
Optionally, step (4) is carried out：Reclaim the lithium in lithium-containing solution.
25. method according to claim 24, it is characterised in that step (1) lithium ion cell anode waste is dried
Reacted again with the organic acid soln containing reducing agent afterwards.
26. method according to claim 25, it is characterised in that the temperature of the drying is 60~200 DEG C, when dry
Between be 6~24h.
27. method according to claim 25, it is characterised in that the drying is convection drying or dried after broken.
28. method according to claim 27, it is characterised in that described to be broken for crushing lithium ion cell anode waste
Into 5mm~15mm × 5mm~15mm fragment.
29. method according to claim 27, it is characterised in that described to be broken for crushing lithium ion cell anode waste
Into 10mm × 10mm fragment.
30. method according to claim 24, it is characterised in that in step (1) described lithium ion cell anode waste
Active material is any of LiFePO4, nickel-based oxide, cobalt base oxide or manganese-base oxide or at least two group
Close.
31. method according to claim 24, it is characterised in that in step (1) described lithium ion cell anode waste
Active material is cobalt acid lithium, lithium nickelate, LiMn2O4, binary composite positive pole or one kind in ternary composite cathode material or extremely
Few two kinds combination.
32. method according to claim 31, it is characterised in that the binary composite positive pole is LiNixCo1–xO2、
LiNixMn1–xO2Or LiCo1–xMnxO2In one kind or at least two combination, wherein, 0<x<1.
33. method according to claim 31, it is characterised in that the ternary composite cathode material is LiNixCoyMnl–x– yO2And/or LiNixCoyAll–x–yO2, wherein, 0<x<1,0<y<1, and 0<x+y<1.
34. method according to claim 24, it is characterised in that step (1) described lithium ion cell anode waste is with containing
The solid-to-liquid ratio for having the organic acid soln of reducing agent is 50~100gL-1。
35. method according to claim 24, it is characterised in that step (1) described lithium ion cell anode waste is with containing
The temperature for having the organic acid soln reaction of reducing agent is 30~70 DEG C.
36. method according to claim 24, it is characterised in that step (1) described lithium ion cell anode waste is with containing
The time for having the organic acid soln reaction of reducing agent is 10~30min.
37. method according to claim 24, it is characterised in that step (1) described lithium ion cell anode waste is with containing
The reaction for having the organic acid soln of reducing agent is carried out under agitation, and mixing speed is 100~500rpm.
38. method according to claim 24, it is characterised in that organic acid in the organic acid soln described in step (1)
Concentration is 2.0~4.0molL-1。
39. method according to claim 24, it is characterised in that the matter of reducing agent in step (1) described organic acid soln
It is 2~6% to measure percentage composition.
40. method according to claim 24, it is characterised in that step (1) described separation of solid and liquid is filtering or centrifugation point
From.
41. method according to claim 24, it is characterised in that step (1) described organic carboxyl acid is formic acid, acetic acid, third
Any of acid, butyric acid or valeric acid or at least two combination.
42. method according to claim 24, it is characterised in that the substituent is fluorine and chlorine.
43. method according to claim 24, it is characterised in that the number of the substituent is 1~9.
44. method according to claim 24, it is characterised in that the number of the substituent is 3~6.
45. method according to claim 24, it is characterised in that step (1) described reducing agent is hydrogen peroxide.
46. method according to claim 24, it is characterised in that step (1) described filter residue is again with containing reducing agent
Organic acid soln is reacted.
47. method according to claim 24, it is characterised in that Ni, Co, Mn or M in step (2) the regulation leachate
In one kind or at least two elements content for into the leachate add nickel water soluble salt, the water soluble salt of cobalt, manganese
Water soluble salt or M water soluble salt in one kind or at least two composition.
48. method according to claim 47, it is characterised in that the water soluble salt of the nickel, the water soluble salt of cobalt, manganese
Anion in water soluble salt or M water soluble salt independently be chlorion, sulfate ion, nitrate ion, acetate from
Any of son or oxalate denominationby or at least two.
49. method according to claim 24, it is characterised in that the system of step (3) the positive active material presoma
Preparation Method is coprecipitation.
50. method according to claim 24, it is characterised in that the lithium that step (4) is described to be reclaimed in lithium-containing solution is：To
Water soluble carbonate, water-soluble phosphate or soluble fluoride are added in lithium-containing solution, and carries out separation of solid and liquid.
51. method according to claim 50, it is characterised in that the water soluble carbonate, water-soluble phosphate or water
Cation in dissolubility fluoride independently is one kind or at least two combination in sodium, potassium or ammonium ion.
52. method according to claim 24, it is characterised in that methods described also includes step (5)：Utilize step (4)
The positive active material presoma that the lithium that recovery is obtained is obtained with step (3) prepares active substance of lithium ion battery anode.
53. method according to claim 52, it is characterised in that the active substance of lithium ion battery anode passes through high temperature
Solid phase reaction is prepared.
54. method according to claim 53, it is characterised in that the temperature of the high temperature solid state reaction is 800~900
℃。
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