CN109896544A - Recycle the method that waste and old lithium titanate anode material prepares metallurgical titanium dioxide and battery-level lithium carbonate - Google Patents
Recycle the method that waste and old lithium titanate anode material prepares metallurgical titanium dioxide and battery-level lithium carbonate Download PDFInfo
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Abstract
The present invention discloses the method that waste and old lithium titanate anode material prepares metallurgical titanium dioxide and battery-level lithium carbonate that recycles, comprising the following steps: A. is broken apart；B. diluted acid heating is leached；C. roasting removes carbon；D. neutral removal of impurities；E. alkalization removal of impurities；F. it is concentrated by evaporation；G. soda ash sinker.The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate, for prior art, hydrogen peroxide is not used in acidleach process, reduces acidleach cost；Dedoping step does not use extraction process, and process flow is shortened, easy to operate；And high income, good product quality；Low, process is short, the advantages such as easily separated, high-efficient, easy to operate, environmentally protective with putting into, and has stronger social value and considerable economic benefit.
Description
Technical field
The present invention relates to waste and old lithium ion battery utilization technology fields, more particularly to a kind of waste and old lithium titanate of recycling
The method that negative electrode material prepares metallurgical titanium dioxide and battery-level lithium carbonate.
Background technique
An important factor for lithium ion battery negative material is as lithium ion secondary battery energy and cycle life is improved, it is alive
Extensive research has been obtained within the scope of boundary.Lithium ion battery negative material is mainly carbon material at present, wherein graphitized carbon application
Most extensively, but graphite and the organic solvent intermiscibility in battery are poor, will limit the charge-discharge performance of battery, and due to graphite
Interlamellar spacing is excessive, and electrolyte and lithium ion are easy to be embedded into graphite layers altogether, and matrix is caused to expand and influence battery life.
Lithium titanate has three-dimensional lithium ion diffusion admittance specific to spinel structure, has excellent power characteristic and excellent
The advantages that good high temperature performance.Compared with carbon negative pole material, the current potential of lithium titanate is high (1.55V higher than the current potential of lithium metal),
The solid-liquid layer as electrolyte and the formation of Carbon anode surface cannot be formed substantially on lithium titanate surface.In the voltage that normal battery uses
In range, Li dendrite is difficult to generate on lithium titanate surface, this is just largely eliminated by Li dendrite in inside battery
Formed short circuit a possibility that, so lithium titanate battery have the characteristics that have extended cycle life it is excellent with security performance, can ensure fastly
The durability of speed charging application field battery and safety.It therefore, is the lithium ion battery of cathode in electric car using lithium titanate
It is required that the application field of high security, high stability and long life cycle has unique advantage.With new-energy automobile market
Expansion and energy storage device gradually exploitation, lithium titanate battery will also be more widely used and growth more rapidly, therewith
And what is come is exactly that the learies of lithium titanate battery increase year by year.
There are three types of waste and old lithium titanate main sources: 1) lithium titanate battery scrap or underproof；2) underproof metatitanic acid
Pole piece (such as producer is in process of production because of the leftover pieces in the unqualified pole piece and production process of a variety of causes production)；
3) underproof lithium titanate powder etc..
In recent years, numerous researchers have done a large amount of work to the recycling and utilization of waste and old lithium titanate anode material.
Chinese Patent Application No. CN201110233096.2 discloses a kind of regeneration side of negative electrode material of waste lithium ion battery lithium titanate
Method.Leach to obtain leachate the method includes acid system, the heated hydrolysis of leachate separates titanium, lithium, filtrate through removal of impurities, concentration,
Sinker obtains lithium carbonate, and metatitanic acid mixes in proportion with lithium carbonate, and sintering prepares lithium titanate anode material.The patent first leaching completely
It does titanium, lithium separation again out, and is related to the techniques such as abstraction impurity removal, cost recovery is higher, complex process, it is difficult to realize industrialization.In
State number of patent application CN201611245696.X discloses a kind of recoverying and utilizing method of waste and old lithium titanate.The method includes
Leachate, leachate and precipitant mix are obtained by peroxide root complexation leaching under alkaline condition, finally obtained after ageing, filtering
Lithium carbonate finally obtains titanium dioxide after the heated hydrolysis of filtrate, roasting.The patent is related to hydrogen peroxide complexation leaching, is produced into
This height and higher to manufacturing technique requirent, sinker process titanium, lithium separating difficulty are larger, and there are no removal of impurities process, product quality
It is difficult to ensure.Chinese Patent Application No. 201711339874.X discloses a kind of recovery method of waste and old lithium titanate anode piece.Institute
The method of stating includes that lithium titanate anode piece ultrasonic vibration is obtained to lithium titanate powder, and lithium titanate powder is through concentrated sulfuric acid dump leaching, abstraction impurity removal, water
Heavy titanium, evaporative crystallization are solved, metatitanic acid and lithium sulfate are finally obtained.The patent, which is related to, destroys lithium titanate structure by concentrated sulfuric acid dump leaching,
The consumption of acid is excessive, while being related to abstraction impurity removal, complex process, and production cost is higher.
Summary of the invention
The present invention is completed to solve in the prior art insufficient, and the object of the present invention is to provide what is more optimized
Lithium titanate anode material recovery process.Compared with the prior art, acidleach process be not used hydrogen peroxide, reduce acidleach at
This；Dedoping step does not use extraction process, and process flow is shortened；And high income, good product quality.It is negative to recycle waste and old lithium titanate
The method that pole material prepares metallurgical titanium dioxide and battery-level lithium carbonate, this method is short, easily separated with process, investment is low,
The advantages such as high-efficient, easy to operate, environmentally protective have stronger social value and considerable economic benefit.
The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate,
The following steps are included:
A. broken apart: negative electrode material of waste lithium ion battery drying, first broken, screening process are isolated into lithium titanate powder
End and aluminium foil.Specifically: by waste and old lithium titanate anode material far-infrared rays drying, remaining electrolyte in negative electrode material is removed in baking
Equal organic matters；It is mechanically pulverized again with crusher, is detached from lithium titanate powder from aluminium foil；Most isolated afterwards through Vibration Screen point
Lithium titanate powder and aluminium foil.
B. diluted acid heating is leached: metering diluted acid being added into the lithium titanate powder that step A obtains, controls Li in material+With
H in diluted acid+Molar ratio be 1:1, solid-to-liquid ratio 1:4~1:5, under conditions of 90~100 DEG C stir 2~5h, control material
PH value 0.5~1.5, leach completely after filters pressing, obtain lithium-containing solution and acid leaching residue, wherein solid-to-liquid ratio be solid phase liquid phase quality
Than；
C. roasting removes carbon: the acid leaching residue that step B is obtained roasts 1 after washing at least twice, then through 600~700 DEG C
~3h removes the carbon dust in acid leaching residue, and obtains titania powder；
D. neutral removal of impurities: in the lithium-containing solution obtained to step B plus alkali adjusts pH value to neutrality, is stirred to react at normal temperature
30~60min removes the Al in pickle liquor3+Ion, filters pressing obtain neutral filtrate and hydroxide aluminium slag；
E. alkalization removal of impurities: being added inorganic base and adjust pH value of solution to 12~13 in the neutral filtrate obtained to step D, 50~
30~60min is stirred under the conditions of 80 DEG C, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag, and the alkalization removal of impurities slag is after sizing mixing
Return step D is recycled；
F. be concentrated by evaporation: by the heating evaporation of scavenging solution containing lithium obtained by step E be concentrated into mother liquor Li ion concentration for 25~
35g/L obtains concentrate containing lithium；
G. the soda ash of metering soda ash sinker: is added by the reaction equation of step G into the concentrate containing lithium that step F is obtained
Solution reacts 1.0~2.0h under the conditions of 90~100 DEG C, after fully reacting through centrifuge separation, wash, be dried to obtain LITHIUM BATTERY
Lithium carbonate.
The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate,
It is heated and is leached by diluted acid, separate titanium, lithium in leaching stage, titanium enters acidleach slag phase, lithium enters acidleach water phase.Acid leaching residue is through roasting
Titanium dioxide is obtained after burn off carbon, battery-level lithium carbonate is prepared through removal of impurities in pickle liquor.The waste and old lithium titanate of recycling of the invention
The method that negative electrode material prepares metallurgical titanium dioxide and battery-level lithium carbonate, compared with the prior art for have the advantage, that
Hydrogen peroxide is not used in acid leaching stage, reduces acidleach cost；Dedoping step does not use extraction process, and process flow is shortened；And
And high income, good product quality.It recycles waste and old lithium titanate anode material and prepares metallurgical titanium dioxide and battery-level lithium carbonate
Method, this method have the advantages such as process is short, easily separated, investment is low, high-efficient, easy to operate, environmentally protective, have stronger
Social value and considerable economic benefit.
Detailed description of the invention
Fig. 1 present invention recycles the method that waste and old lithium titanate anode material prepares metallurgical titanium dioxide and battery-level lithium carbonate
Flow chart.
Fig. 2 is lithium titanate powder XRD diagram；
Fig. 3 is that roasting obtains titanium dioxide XRD diagram.
Specific embodiment
Fig. 1 to Fig. 3 with reference to the accompanying drawing and specific embodiment are to the waste and old lithium titanate anode material of recycling of the invention
The method for preparing metallurgical titanium dioxide and battery-level lithium carbonate is described in further detail.
The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate,
Referring to FIG. 1, the following steps are included:
A. broken apart: negative electrode material of waste lithium ion battery drying, first broken, screening process are isolated into lithium titanate powder
End and aluminium foil.Specifically: by waste and old lithium titanate anode material far-infrared rays drying, remaining electrolyte in negative electrode material is removed in baking
Equal organic matters；It is mechanically pulverized again with crusher, is detached from lithium titanate powder from aluminium foil；Most isolated afterwards through Vibration Screen point
Lithium titanate powder and aluminium foil.
B. diluted acid heating is leached: metering diluted acid being added into the lithium titanate powder that step A obtains, controls Li in material+With
H in diluted acid+Molar ratio be 1:1, solid-to-liquid ratio 1:4~1:5, under conditions of 90~100 DEG C stir 2~5h, control material
PH value 0.5~1.5, leach completely after filters pressing, obtain lithium-containing solution and acid leaching residue, wherein solid-to-liquid ratio be solid-liquid mass ratio；
C. roasting removes carbon: the acid leaching residue that step B is obtained roasts 1 after washing at least twice, then through 500~700 DEG C
~3h removes the carbon dust in acid leaching residue, and obtains titania powder；
D. neutral removal of impurities: in the lithium-containing solution obtained to step B plus alkali adjusts pH value to neutrality, is stirred to react at normal temperature
30~60min removes the Al in pickle liquor3+Ion, filters pressing obtain neutral filtrate and hydroxide aluminium slag；
E. alkalization removal of impurities: being added inorganic base and adjust pH value of solution to 12~13 in the neutral filtrate obtained to step D, 50~
30~60min is stirred under the conditions of 80 DEG C, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag, and the alkalization removal of impurities slag is after sizing mixing
Return step D is recycled；
F. be concentrated by evaporation: by the heating evaporation of scavenging solution containing lithium obtained by step E be concentrated into mother liquor Li ion concentration for 25~
35g/L obtains concentrate containing lithium；
G. soda ash sinker: based on being added into the concentrate containing lithium that step F is obtained by the step G reaction equation of listed thereafter
The soda ash solution of amount, metering is so that lithium ion and the Na in soda ash solution2CO3Fully reacting is formed subject to lithium carbonate precipitating,
1.0~2.0h is reacted under the conditions of 90~100 DEG C, after fully reacting through centrifuge separation, wash, be dried to obtain battery-level lithium carbonate.
The ion-reaction equation of the step B are as follows:
Li4Ti5O12+4H+==4Li++5TiO(OH)2+2H2O
2Al+6H+==2Al3++3H2↑
The step of acid dipping can make titanium, lithium separation under diluted acid heating condition, and titanium enters slag phase, and lithium enters water phase.
The reaction equation of the step C are as follows:
C+O2==CO2↑
TiO(OH)2==TiO2+H2O
The step under the high temperature conditions, makes metatitanic acid be dehydrated to obtain titanium dioxide product while except carbon.
The ion-reaction equation of the step D are as follows:
Al3++3OH—==Al (OH)3↓
The ion-reaction equation of the step E are as follows:
Mg2++2OH—==Mg (OH)2↓
The ion-reaction equation of the step G are as follows:
2Li++Na2CO3==Li2CO3↓+2Na+
The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate
Lixiviation process is heated by diluted acid, separates titanium, lithium in leaching stage, titanium enters in acid leaching residue, lithium enters in pickle liquor, acid leaching residue roasting
Titanium dioxide is obtained after burn off carbon, battery-level lithium carbonate is prepared through removal of impurities in pickle liquor.The waste and old lithium titanate of recycling of the invention
The method that negative electrode material prepares metallurgical titanium dioxide and battery-level lithium carbonate, compared with the prior art for have the advantage, that
Hydrogen peroxide is not used in acidleach process, reduces acidleach cost, and dedoping step does not use extraction process, compared with the prior art for work
Skill process is shorter, and lithium, titanium separation are simple thorough, and production cost is low, and environmental-friendly, recovery process is few, and the rate of recovery is high, is suitble to industry
Metaplasia produces.There are the advantages such as process is short, easily separated, investment is low, high-efficient, easy to operate, environmentally protective simultaneously, have stronger
Social value and considerable economic benefit.
The method that the waste and old lithium titanate anode material of recycling of the invention prepares metallurgical titanium dioxide and battery-level lithium carbonate,
Referring to FIG. 1, specifically may is that the step A drying temperature is 150~200 DEG C on the basis of technical solution in front, drying
Time is 0.5~1.0h, smashes it through 20~80 meshes.Under the conditions of the drying temperature and drying time, electrolyte can be made
Completely, and unlikely temperature is excessively high keeps aluminium foil brittle, separates difficulty with lithium titanate powder so as to cause aluminium foil for volatilization drying.Due to aluminium
Foil has certain ductility, and the aluminium foil fragment obtained after broken is larger, aluminium foil and lithium titanate powder can be made abundant through 20~80 meshes
Separation, aluminium foil stay on sieve, and lithium titanate powder is under sieve.
It may also is that diluted acid is at least one of hydrochloric acid, sulfuric acid, nitric acid in the step B.These types of acid is laboratory
Common inorganic acid provides hydrogen ion for acid-leaching reaction.
It may also is that the maturing temperature of the step C is 600~700 DEG C, metatitanic acid is set to be converted into two under the conditions of the temperature
Titanium oxide, while roasting process can blast air or oxygen with air blower, to promote carbon dust full combustion.
It may also is that the alkali of the step D is at least one of magnesium hydroxide, liquid alkaline, soda ash, ammonium hydroxide.These types of alkali
Adjustable pickle liquor pH promotes trivalent aluminium ion hydrolysis in solution to generate aluminum hydroxide precipitation to neutrality, while will not introduce it
Its impurity or introducing impurity are less.
It may also is that the inorganic base in the step E is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide.
Magnesium ion, calcium ion in solution etc. can be made to form magnesium hydroxide, calcium hydroxide precipitation under strongly alkaline conditions, to reach net
Change the purpose of solution, while other impurity will not be introduced.
It may also is that the soda ash solution concentration in the step G is 180~220g/L.Under the concentration conditions, sinker mother liquor
Less, a sinker high income is measured, while being unlikely to excessive concentration causes product sodium content high, influences product quality.
Embodiment 1:
A. broken apart: negative electrode material of waste lithium ion battery drying, crushing, screening process are isolated into lithium titanate powder
End and aluminium foil, lithium titanate powder XRD data reference Fig. 2.
B. diluted acid heating is leached: weighing lithium titanate powder 100kg obtained by step A, wherein lithium content is 4.05% for analysis, titanium
Content is 34.71%, Al content 0.9%, and the hydrochloric acid 69.1kg that weight ratio is 31%, pure water are added into lithium titanate powder
450kg, solid-to-liquid ratio 1:4.5, by slurry be heated to 100 DEG C and stir 3 hours, leach completely after filters pressing, obtain lithium-containing solution and
Acid leaching residue.
C. roasting removes carbon: twice, in 600 DEG C of roasting 2h, roasting process is constantly passed through for the acid leaching residue washing that step B is obtained
Air obtains titania powder 56.8kg after roasting completely, and titanium dioxide ingredient is shown in Table 1, titania powder XRD number
According to reference Fig. 3.Titanium dioxide quality meets YS/T322-2015 metallurgy titanium dioxide standard requirements.
D. neutral removal of impurities: (Li 9.3g/L, Al 2.0g/L, Ti are the 430L lithium-containing solution obtained to step B
In 0.009g/L) plus magnesium hydroxide slurry tune pH value is to neutrality, is stirred to react 30min at normal temperature, filters pressing obtains neutral filtrate
With hydroxide aluminium slag.
E. alkalization removal of impurities: in the neutral filtrate obtained to step D be added weight ratio be 32% liquid alkaline adjust pH value of solution to
13,30min is stirred under the conditions of 80 DEG C, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag.Alkalization removal of impurities slag can after sizing mixing
Return step D is recycled.
F. it is concentrated by evaporation: the heating evaporation of scavenging solution containing lithium obtained by step E being concentrated into 153L, Li ion concentration in concentrate
For 26.0g/L, concentrate containing lithium is obtained.
G. soda ash sinker: 163L concentration, which is added, by step G reaction equation into the concentrate containing lithium that step F is obtained is
The soda ash solution of 220g/L is stirred to react 2.0h under the conditions of 90 DEG C, after fully reacting through centrifugation, wash, be dried to obtain battery
The chemical component of level lithium carbonate 20.8kg, lithium carbonate are shown in Table 2.Lithium carbonate quality meets YS/T 582-2006 battery grade standard and wants
It asks.
Embodiment 2:
A. broken apart: the processes such as negative electrode material of waste lithium ion battery drying, crushing, screening are isolated into lithium titanate
Powder and aluminium foil；
B. diluted acid heating is leached: weighing lithium titanate powder 100kg obtained by step A, wherein lithium content is 3.99% for analysis, titanium
Content is 34.2%, Al content 1.0%, and the sulfuric acid 148kg that weight ratio is 20%, pure water are added into lithium titanate powder
500kg, solid-to-liquid ratio 1:5, are heated to 100 DEG C for slurry and stir 2 hours, and filters pressing after leaching completely obtains lithium-containing solution and acid
Phase analysis.
C. roasting removes carbon: twice, in 650 DEG C of roasting 3h, roasting process is constantly passed through for the acid leaching residue washing that step B is obtained
Air obtains titania powder 55.9kg after roasting completely, and titanium dioxide ingredient is shown in Table 1.Titanium dioxide quality meets
YS/T 322-2015 metallurgy titanium dioxide standard requirements.
D. neutral removal of impurities: (Li 9.6g/L, Al 2.4g/L, Ti are the 410L lithium-containing solution obtained to step B
In 0.011g/L) plus soda ash solution tune pH value is to neutrality, is stirred to react 50min at normal temperature, filters pressing obtains neutral filtrate and hydrogen
Aoxidize aluminium slag.
E. alkalization removal of impurities: potassium hydroxide solution is added in the neutral filtrate obtained to step D and adjusts pH to 12, in 70 DEG C of items
30min is stirred under part, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag.
F. it is concentrated by evaporation: the heating evaporation of scavenging solution containing lithium obtained by step E being concentrated into 120L, Li ion concentration in concentrate
For 32.5g/L, concentrate containing lithium is obtained.
G. soda ash sinker: 170L concentration, which is added, by step G reaction equation into the concentrate containing lithium that step F is obtained is
The soda ash solution of 205g/L is stirred to react 1.5h under the conditions of 95 DEG C, after fully reacting through centrifugation, wash, be dried to obtain battery
The chemical component of level lithium carbonate 20.4kg, lithium carbonate are shown in Table 2.Lithium carbonate quality meets YS/T 582-2006 battery grade standard and wants
It asks.
Embodiment 3:
A. broken apart: the processes such as negative electrode material of waste lithium ion battery drying, crushing, screening are isolated into lithium titanate
Powder and aluminium foil；
B. diluted acid heating is leached: weighing lithium titanate powder 100kg obtained by step A, wherein lithium content is 4.06% for analysis, titanium
Content is 34.8%, Al content 0.8%, and the nitric acid 194kg that weight ratio is 20%, pure water are added into lithium titanate powder
400kg, solid-to-liquid ratio 1:4, are heated to 95 DEG C for slurry and stir 4 hours, and filters pressing after leaching completely obtains lithium-containing solution and acidleach
Slag.
C. roasting removes carbon: twice, in 700 DEG C of roasting 3h, roasting process is constantly passed through for the acid leaching residue washing that step B is obtained
Oxygen obtains titania powder 56.4kg after roasting completely, and titanium dioxide ingredient is shown in Table 1.Titanium dioxide quality meets
YS/T 322-2015 metallurgy titanium dioxide standard requirements.
D. neutral removal of impurities: (Li 10.6g/L, Al 1.9g/L, Ti are the 380L lithium-containing solution obtained to step B
Ammonification aqueous solution tune pH value is stirred to react 60min, filters pressing obtains neutral filtrate and hydrogen to neutrality at normal temperature in 0.003g/L)
Aoxidize aluminium slag.
E. alkalization removal of impurities: lithium hydroxide solution is added in the neutral filtrate obtained to step D and adjusts pH to 13, in 60 DEG C of items
30min is stirred under part, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag.
F. it is concentrated by evaporation: the heating evaporation of scavenging solution containing lithium obtained by step E being concentrated into 128L, Li ion concentration in concentrate
For 31.2g/L, concentrate containing lithium is obtained.
G. soda ash sinker: 204L concentration, which is added, by step G reaction equation into the concentrate containing lithium that step F is obtained is
The soda ash solution of 180g/L is stirred to react 2h under the conditions of 95 DEG C, after fully reacting through centrifugation, wash, be dried to obtain LITHIUM BATTERY
The chemical component of lithium carbonate 20.8kg, lithium carbonate are shown in Table 2.Lithium carbonate quality meets YS/T 582-2006 LITHIUM BATTERY standard requirements.
Embodiment 4:
A. broken apart: the processes such as negative electrode material of waste lithium ion battery drying, crushing, screening are isolated into lithium titanate
Powder and aluminium foil；
B. diluted acid heating is leached: weighing lithium titanate powder 100kg obtained by step A, wherein lithium content is 3.88% for analysis, titanium
Content is 33.3%, Al content 0.9%, and the hydrochloric acid 69.0kg that weight ratio is 31%, pure water are added into lithium titanate powder
450kg, solid-to-liquid ratio 1:4.5, are heated to 95 DEG C for slurry and stir 4 hours, and filters pressing after leaching completely obtains lithium-containing solution and acid
Phase analysis.
C. roasting removes carbon: twice, in 700 DEG C of roasting 1h, roasting process is constantly passed through for the acid leaching residue washing that step B is obtained
Oxygen obtains titania powder 54.5kg after roasting completely, and titanium dioxide ingredient is shown in Table 1.Titanium dioxide quality meets
YS/T 322-2015 metallurgy titanium dioxide standard requirements.
D. neutral removal of impurities: (Li 9.8g/L, Al 2.2g/L, Ti are the 390L lithium-containing solution obtained to step B
Adding sodium hydroxide solution tune pH value is stirred to react 60min, filters pressing obtains neutral filtrate to neutrality at normal temperature in 0.005g/L)
With hydroxide aluminium slag.
E. alkalization removal of impurities: sodium hydroxide solution is added in the neutral filtrate obtained to step D and adjusts pH to 13, in 80 DEG C of items
30min is stirred under part, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag.
F. it is concentrated by evaporation: the heating evaporation of scavenging solution containing lithium obtained by step E being concentrated into 130L, Li ion concentration in concentrate
For 29.1g/L, concentrate containing lithium is obtained.
G. soda ash sinker: 158L concentration, which is added, by step G reaction equation into the concentrate containing lithium that step F is obtained is
The soda ash solution of 220g/L is stirred to react 1h under the conditions of 100 DEG C, after fully reacting through centrifugation, wash, be dried to obtain LITHIUM BATTERY
The chemical component of lithium carbonate 19.8kg, lithium carbonate are shown in Table 2.Lithium carbonate quality meets YS/T 582-2006 LITHIUM BATTERY standard requirements.
1 titanium dioxide product technical indicator (mass percentage %) of table
2 battery-level lithium carbonate technical target of the product (mass percentage %) of table
It is above-mentioned that only several specific embodiments in the present invention are illustrated, but can not be as protection model of the invention
Enclose, it is all according to the present invention in design spirit made by equivalent change or modification or equal proportion zoom in or out, should all
Think to fall into protection scope of the present invention.
Claims (7)
1. recycling the method that waste and old lithium titanate anode material prepares metallurgical titanium dioxide and battery-level lithium carbonate, including following step
It is rapid:
A. broken apart: by negative electrode material of waste lithium ion battery drying, crushing, screening process isolate lithium titanate powder and
Aluminium foil；
B. diluted acid heating is leached: metering diluted acid being added into the lithium titanate powder that step A obtains, controls Li in material+In diluted acid
H+Molar ratio be 1:1, solid-to-liquid ratio 1:4~1:5, under conditions of 90~100 DEG C stir 2~5h, control the pH value of material
0.5~1.5, filters pressing after leaching completely obtains lithium-containing solution and acid leaching residue, and wherein solid-to-liquid ratio is solid phase liquid phase quality ratio；
C. roasting removes carbon: the acid leaching residue that step B is obtained after washing at least twice, then through 600~700 DEG C of 1~3h of roasting,
The carbon dust in acid leaching residue is removed, and obtains titania powder；
D. neutral removal of impurities: in the lithium-containing solution obtained to step B plus alkali adjusts pH value to neutrality, it is stirred to react 30 at normal temperature~
60min removes the Al in pickle liquor3+Ion, filters pressing obtain neutral filtrate and aluminium hydroxide filter residue；
E. alkalization removal of impurities: inorganic base is added in the neutral filtrate obtained to step D and adjusts pH value of solution to 12~13, at 50~80 DEG C
Under the conditions of stir 30~60min, filters pressing obtains scavenging solution containing lithium and alkalization removal of impurities slag, and the alkalization slag that cleans returns after sizing mixing
Step D is recycled；
F. it is concentrated by evaporation: the heating evaporation of scavenging solution containing lithium obtained by step E is concentrated into Li in mother liquor+Ion concentration is 25~35g/
L obtains concentrate containing lithium；
G. soda ash sinker: the soda ash solution of metering is added into the concentrate containing lithium that step F is obtained, under the conditions of 90~100 DEG C
React 1.0~2.0h, after fully reacting through centrifuge separation, wash, be dried to obtain battery-level lithium carbonate.
2. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: the step A drying temperature is 150~200 DEG C, and drying time is 0.5~1.0h, after crushing
Cross 20~80 meshes.
3. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: diluted acid is at least one of hydrochloric acid, sulfuric acid, nitric acid in the step B.
4. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: the maturing temperature of the step C is 600~700 DEG C, and roasting process can be blasted with air blower
Air or oxygen.
5. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: the alkali of the step D is at least one of magnesium hydroxide, liquid alkaline, soda ash, ammonium hydroxide.
6. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: inorganic base in the step E is sodium hydroxide, potassium hydroxide, at least one in lithium hydroxide
Kind.
7. the waste and old lithium titanate anode material of recycling according to claim 1 prepares metallurgical titanium dioxide and LITHIUM BATTERY carbonic acid
The method of lithium, it is characterised in that: the soda ash solution concentration of the step G is 180~220g/L.
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