CN107754771B - A kind of bark ion colloidal sol and preparation method and application for lithium battery recycling - Google Patents
A kind of bark ion colloidal sol and preparation method and application for lithium battery recycling Download PDFInfo
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Abstract
The present invention relates to a kind of bark ion colloidal sols and preparation method and application for lithium battery recycling, belong to lithium ion battery recovery technology field.The technical problem to be solved by the present invention is to provide a kind of preparation methods of bark ion colloidal sol for lithium battery recycling.After this method pre-processes bark, highly polar ionic liquid is dissolved under microwave heating condition and then activates swelling, after vacuum distillation to obtain the final product.Bark ion colloidal sol is prepared as raw material using bark in the present invention, and raw material sources are extensive, and preparation process is simple, and cost is relatively low.The bark ion colloidal sol being prepared, with stronger Selective adsorption, alternative Al adsorption, nickel, copper metal, it can be directly used for adsorption recovery lithium battery anode solution, the means such as separate without high-temperature calcination or soda acid to separate the various precious metal materials in anode material for lithium-ion batteries, its recovery method is simple, and process safety is pollution-free, low in cost.
Description
Technical field
The present invention relates to a kind of bark ion colloidal sol and its preparation method and application for lithium battery recycling, belong to lithium from
Sub- battery recycling technical field.
Background technique
Lithium ion battery is a series of green battery with excellent performances, since realizing commercialization at the end of the 20th century, with
It has many advantages, such as big energy density, light weight, long and without memory service life, is widely used in electric bicycle, electricity
The power batteries such as power driven tools, vehicle using motor, golf cart, ship model toy, mine lamp field, mobile phone, laptop, photograph
In the field of portable electronic apparatus such as machine and electric car.The following material is in fields such as mobile communication base station, energy storage devices
Also there is development space.
The positive electrode of lithium ion battery has very much, in currently in use and exploitation anode material of lithium battery, with mistake
It is best to cross the performance that metal oxide is shown, mainly has：The cobalt acid lithium of bedded salt structure, lithium nickel cobalt dioxide, nickel ion doped and
Nickel manganese cobalt acid lithium ternary material, the LiMn2O4 of spinel-type, the lithium manganese oxides such as LiFePO4 of olivine-type.China is current just
Pole material mainly includes cobalt acid lithium, ternary material, LiMn2O4 and LiFePO4.It, will be big with the extensive use of lithium ion battery
Amount enters failure, recovery stage.How to recycle waste and old lithium ion battery and resource recycling utilizes and has become social common concern
The problem of.
Patent of invention CN104577248A discloses a kind of anode material of lithium battery recovery method, and this method includes following step
Suddenly：A. aqueous slkali soaking：Discarded anode material of lithium battery positive plate is placed in the container for fill alkaline solution and is impregnated,
Obtain aluminium hydroxide and cobalt acid lithium powder；B. it hydrolyzes：By the mixing of aluminum hydroxide solution obtained in the previous step and cobalt acid lithium powder
Liquid is placed in pure water to be hydrolyzed and then carries out obtaining cobalt acid lithium powder after water sieve washes；C. hydrogenation treatment：Step a will be passed through
It is put into atmosphere furnace with the cobalt acid lithium powder obtained after b processing, hydrogen is then filled in furnace by high-temperature heating, is hydrogenated
Cobalt acid lithium afterwards；D. hydrolysis removes lithium：Cobalt acid lithium after hydrogenation is put into pure water and is hydrolyzed, the solution after being hydrolyzed；E.
It is separated by solid-liquid separation：The cobalt acid lithium after hydrogenation is separated by solid-liquid separation by separator, and three times by the solid washing after separation, so
After dry, crushing finally obtain the cobalt oxide that can be used as anode material of lithium battery.
Patent of invention CN107275702A discloses a kind of recovery method of waste and old ternary battery.This method includes following step
Suddenly：(1) anode pole piece will be taken to wash after the dismantling of waste and old ternary battery, then carries out high-temperature process；It (2) will be through step (1) high temperature
Treated, and anode pole piece crushes；It is placed in organic acid soln system again and reacts to obtain reaction solution；The organic acid soln system
Include：Malic acid, succinic acid, ascorbic acid and H2O2；(3) extract liquor is added in the reaction solution described in step (2) to be extracted
It takes, separating and extracting liquid after extraction；The extract liquor includes kerosene and tributyl phosphate；(4) it is added in extract liquor inorganic
Acid solution is simultaneously fullyd shake, and inorganic acid solution is separated after concussion；(5) saturated sodium carbonate is added in inorganic acid solution
Solution obtains sediment lithium carbonate.
As it can be seen that the above method mainly separates lithium ion cell positive by the means such as high-temperature calcination or soda acid separation
Various precious metal materials in material.Generally existing energy consumption is high, process is tedious, serialization degree is low, and soda acid is separated to body
Endanger the disadvantages of big.Therefore, a kind of method of new recycling anode material of lithium battery is needed.
It is a kind of newer recovery technology that biological adsorption, which recycles metal, can choose adsorptivity with suitable biomaterial
Absorption and recycling metal ion.Patent of invention 106975468A discloses a kind of for recycling the lithium metal in lithium ion battery
Cellulosic material and preparation method thereof, the cellulosic material are prepared by following steps：(1) by cellulose and sodium methoxide
It is added in dehydrated alcohol, is uniformly mixed, obtains mixture A；(2) 3,5- dimethyl ester yl benzoic acid is added in mixture A,
And be stirred to react in ice bath 2-4 hours, it filters, obtains compound B；(3) solvent is added in the compound B and straight chain ketone
In, catalyst is added, under the conditions of 20-40 DEG C of temperature, is stirred to react 4-6h, filters, obtains the cellulosic material.It should
Cellulosic material contains a large amount of hydroxyl, high, nontoxic with preferable hydrophily and porous and large specific surface area, selectivity,
The features such as harmless.But the material only has suction-operated to lithium metal, can not separate the elements such as nickel, the cobalt in lithium battery.
Summary of the invention
For disadvantages described above, the purpose of the present invention is to provide a kind of bark ion colloidal sol for lithium battery recycling and its
Preparation method can efficiently separate copper, cobalt, nickel using the bark ion colloidal sol to the highly selective of ion, so that recycling
Journey is environment friendly and pollution-free.
First technical problem that the present invention solves is to provide a kind of system of bark ion colloidal sol for lithium battery recycling
Preparation Method.
A kind of preparation method of the bark ion colloidal sol for lithium battery recycling of the present invention, includes the following steps：
1）The pretreatment of bark：It is crushed after bark is cleaned, dried, obtains bark fines；
2）The dissolution of bark：Bark fines are dissolved in highly polar ionic liquid under microwave heating condition, filters, is set
Skin solution, wherein the frequency of microwave heating is 400~800MHz；
3）The swelling of bark activates：Sodium hydroxide activation swelling is added in bark solution；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
Not only contain a large amount of cellulose in bark, also there are other nutrition such as pentosan, terpene, sterol and aliphatic ester
Ingredient.Bark ion colloidal sol of the invention is raw material using bark, colloidal cellulose can be prepared by simple process,
Not only contain a large amount of cellulose in the colloidal cellulose, also with other nutritional ingredients in bark, there is stronger selection
Adsorptivity can adsorb aluminium ion, nickel ion and copper ion in anode material for lithium-ion batteries solution.
Bark of the present invention can using commercially available, can also be used fresh bark dry it is obtained.The type of bark does not have
It limits, Chinese scholartree bark, eucalyptus bark, birch number bark, pine bark, maple bark, cinnamomum camphora tree bark, Chinese parasol tree tree tree can be used
Skin, elm bark, oak bark and ginkgo bark etc..
Each step of the method for the present invention is described in detail below.
Step 1）In, the cleaning preferred method of bark is：After bark is rinsed with clear water, be put into acetic acid impregnate 30~
60min.Immersion can soften bark cell wall, so that the nutriment in bark cell is easier to release, after promoting
Continuous dissolution improves the Selective adsorption in lithium ion battery recycling.
It in order to preferably dissolve bark, needs to crush on bark, it is preferred that the partial size of bark fines is less than 20 μm.
The method that bark crushes can use existing method, after can first being crushed with pulverizer, then with ball mill carry out ball
Mill, obtains powder of the partial size less than 20 μm.Pulverizer is the machinery that large-sized solid material is crushed to desired size.It crushes
Machine is made of the devices such as coarse crushing, fine crushing, wind model, and the purpose of pulverizer is reached in the form of high-speed impact.It commonly uses in the market
Pulverizer be suitable for the present invention.And ball mill is the key equipment that material is broken and then is crushed.Ball mill by
Feed portion, discharging portion, rotating part, driving section（Speed reducer, small transmission gear, motor are automatically controlled）Etc. major parts composition.In the market
Common ball mill is also suitable for the present invention.
Step 2）In, bark fines are dissolved in by highly polar solion using the method for microwave heating.Microwave heating is exactly
Using the energy feature of microwave, the process that object is heated.The obvious characteristics such as, frequency high, Quantum Properties short with wavelength.
Microwave heating technique is different from traditional heating mode, it is moved by heated object internal dipole molecule high-frequency reciprocating, generates
" interior frictional heat " and make to be heated temperature of charge raising, be not necessary to any heat transfer process, can make material inside and outside portion and meanwhile heat,
It heats up simultaneously, heating speed is fast and uniformly, it is only necessary to the part of the energy consumption of traditional heating mode or tens/once reachable
To heating purpose.From theory analysis, substance generated amount of heat in microwave field has with substance classes and its dielectric property
Much relations, i.e. microwave have selectivity plus thermal property to substance.The present invention is just able to achieve of the invention using microwave heating
Purpose.In order to dissolve bark to greatest extent, it is preferred that the frequency of microwave heating is 400~800MHz, more preferable microwave heating
Frequency be 600MHz.
The present invention is dissolved in bark in highly polar ionic liquid.Ionic liquid is a kind of in room temperature or close at room temperature
Salt that liquid is presented, being made of completely zwitterion, also referred to as low temperature molten salt.Common highly polar ionic liquid is applicable in
In the present invention.Preferably, the highly polar ionic liquid is 1- butyl -3- methylimidazole villaumite solution.Inventor the study found that
In 1- butyl -3- methylimidazole villaumite solution, water will promote the dissolution of cellulose, and water can also reduce the viscous of ionic liquid
Degree, it is at low cost, it is therefore preferable that containing water in ionic liquid.But when the content of water is more than 5%, the solubility of cellulose is anti-
And can decline or even lose dissolubility, and this is because cellulosic structure high-sequential, intramolecular and intermolecular there are a large amount of hydrogen bonds
With complicated noncrystalline domain.It is preferred, therefore, that the mass percent of water is in the 1- butyl -3- methylimidazole villaumite solution
2~5%.
Step 3）Purpose be by bark solution be swollen activate, can as adsorbent selectivity adsorbing metal from
Son.Since the cellulose in bark solution is not soluble in water, if, containing water, be easy so that fiber in the sodium hydroxide being added
Element is precipitated, and the purpose of swelling activation is not achieved, and therefore, sodium hydroxide used is solid, it is preferred that the additional amount of sodium hydroxide
0.05~0.2g sodium hydroxide is added for every milliliter of bark solution.
Step 4）Vacuum distillation primarily to removal solvent, obtain product colloidal cellulose.Vacuum distillation can adopt
With conventional vacuum distillation equipment, common vacuum distillation method and equipment are suitable for the present invention, and this will not be repeated here.
A kind of preparation method of the bark ion colloidal sol for lithium battery recycling of the present invention, each step complement each other, lack
One can not, using the cellulose in bark be main adsorbent, be aided with pentosan, terpene, sterol and aliphatic ester etc. other
Nutritional ingredient is dissolved post activation, colloidal cellulose is thus prepared.Inventor has found under study for action, the glue fiber
Element being capable of selective absorption aluminium, nickel and copper.
Second technical problem that the present invention solves is to provide bark ion colloidal sol prepared by the preparation method.
Bark ion colloidal sol of the invention has strong Selective adsorption to aluminium, nickel, copper, can adsorb in lithium battery anode solution
Aluminium, nickel, copper metal ion.
The present invention also provides application of the bark ion colloidal sol of the present invention in recycling anode material for lithium-ion batteries.
Bark ion colloidal sol of the present invention, can be used for recycling anode material for lithium-ion batteries.
Preferably, the method recycled is as follows：
A, waste and old lithium ion battery is removed, crushes, obtains positive electrode powder；
B, positive electrode powder is dissolved, obtains positive solution；Wherein, the method for dissolution can use conventional method, than
Such as acid-hatching of young eggs；
C, bark ion colloidal sol is added in positive solution, is warming up to 40~60 DEG C of 30~60min of reaction, filters, obtains
Filter residue 1 and filtrate 1, filter residue 1 recycles aluminium, nickel and copper, after lye or salting liquid precipitate cobalt is added in filtrate 1, filtering, and resulting filtrate
2 be lithium-containing solution.
The method of recycling of the invention is actually biological adsorption recycling metal method.It uses bark as biomaterial, passes through
Bark ion colloidal sol is prepared after processing, the metal ions such as aluminium, nickel and copper are closed in the absorption and recycling for the property of can choose.Used in lithium
In the recycling of ion battery positive electrode, aluminium, nickel, copper and cobalt, the recycling for noble metal in lithium battery can be gone out with simple separation
With important practical significance.
Compared with prior art, the present invention has the advantages that：
1）Bark ion colloidal sol is prepared as raw material using bark in the present invention, and raw material sources are extensive, preparation process
Simply, cost is relatively low.
2）Bark ion colloidal sol of the invention, have stronger Selective adsorption, alternative Al adsorption, nickel, copper metal,
After absorption, the aluminium, nickel and copper content in residual liquid are low, can greatly recycle aluminium, nickel and copper.
3）Bark ion colloidal sol of the invention, can be directly used for adsorption recovery lithium battery anode solution, without high temperature
The means such as calcining or soda acid separation separate the various precious metal materials in anode material for lithium-ion batteries, recovery method letter
Single, process safety is pollution-free, low in cost.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：It is crushed after bark is washed, dried, obtains the bark fines that partial size is 20 μm；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 400MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 2%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.05g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, recovery method is：
A, waste and old lithium ion battery is removed, crushes, obtains positive electrode powder；
B, positive electrode powder is dissolved, obtains positive solution；The ingredient of positive solution is shown in Table 1；
C, bark ion colloidal sol is added in positive solution, is warming up to 50 DEG C of reaction 40min, filters, obtains filter residue and filter
Liquid 1, filter residue can recycle aluminium, nickel and copper, and the ingredient of filtrate 1 is shown in Table 1.
D, sodium hydroxide pellets cobalt is added in filtrate, filtering obtains filter residue and filtrate 2, and filter residue can recycle to obtain cobalt,
The ingredient of filtrate 2 is shown in Table 1.
Embodiment 2
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：It after bark is washed, is put into acetic acid and impregnates 30min, crushed after drying, obtaining partial size is
20 μm of bark fines；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 800MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 3%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.2g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, positive solution prepared by Example 1 adds
Enter bark ion colloidal sol, be warming up to 50 DEG C of reaction 40min, filter, obtain filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Embodiment 3
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：Bark is washed, is put into acetic acid and impregnates 60min, is crushed after drying, obtaining partial size is 20
μm bark fines；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 600MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 5%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.1g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, positive solution prepared by Example 1 adds
Enter bark ion colloidal sol, be warming up to 50 DEG C of reaction 40min, filter, obtain filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Embodiment 4
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：Bark is washed, is put into acetic acid and impregnates 40min, is crushed after drying, obtaining partial size is 20
μm bark fines；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 800MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 4%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.15g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, positive solution prepared by Example 1 adds
Enter bark ion colloidal sol, be warming up to 50 DEG C of reaction 40min, filter, obtain filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Embodiment 5
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：Bark is washed, is put into acetic acid and impregnates 40min, is crushed after drying, obtaining partial size is 20
μm bark fines；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 400MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 2%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.05g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, positive solution prepared by Example 1 adds
Enter bark ion colloidal sol, be warming up to 50 DEG C of reaction 40min, filter, obtain filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Embodiment 6
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：It is crushed after bark is washed, dried, obtains bark fines；
2）The dissolution of bark：Bark fines are dissolved in 1- butyl -3- methylimidazole villaumite solution under microwave heating condition
In, filtering obtains bark solution, wherein the frequency of microwave heating is 700MHz, in 1- butyl -3- methylimidazole villaumite solution
Water weight percent be 3%.
3）The swelling of bark activates：Sodium hydrate solid activation swelling is added in bark solution；The addition of sodium hydroxide
0.15g sodium hydroxide is added for every milliliter of bark solution in amount；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
The bark ion colloidal sol is used in the recycling of anode material of lithium battery, positive solution prepared by Example 1 adds
Enter bark ion colloidal sol, be warming up to 50 DEG C of reaction 40min, filter, obtain filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Comparative example 1
It is prepared as follows to obtain bark ion colloidal sol：
1）The pretreatment of bark：It is crushed after bark is washed, dried, obtains bark fines；
2）The dissolution of bark：By bark fines under microwave heating condition, filtering obtains bark solution, wherein microwave adds
The frequency of heat is 700MHz；
3）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose is obtained, i.e., modified bark colloidal sol.
The bark colloidal sol that embodiment 1-6, comparative example 1 obtain is used in the recycling of anode material of lithium battery, takes anode molten
Liquid is added bark colloidal sol, is warming up to 50 DEG C of reaction 40min, and filtering obtains filter residue and filtrate 1, filter residue can recycle aluminium, nickel and
The ingredient of copper, filtrate 1 is shown in Table 1.Sodium hydroxide pellets cobalt is added in filtrate 1, filtering obtains filter residue and filtrate 2, and filter residue can be with
Recycling obtains cobalt, and the ingredient of filtrate 2 is shown in Table 1.
Table 1
From table 1 it follows that the bark ion colloidal sol prepared using the embodiment of the present invention 1~6, can effectively be adsorbed
Al, Ni and Cu can be recycled, and after remaining Co can be precipitated by conventional method, obtain purer lithium-containing solution.
Wherein, after bark fines being impregnated with acetic acid, the solution adsorption rate of obtained bark ion colloidal sol is higher, the residual in filtrate 1
Tenor is lower.
And compared with the comparative example 1 for using ionic liquid to handle, the selectivity of the bark ion colloidal sol after present invention activation is inhaled
Attached stronger, adsorption rate is higher, and the residual quantity in filtrate 1 is also lower.
Claims (10)
1. a kind of preparation method of the bark ion colloidal sol for lithium battery recycling, which is characterized in that include the following steps：
1）The pretreatment of bark：It is crushed after bark is cleaned, dried, obtains bark fines；
2）The dissolution of bark：Bark fines are dissolved in highly polar ionic liquid under microwave heating condition, filters, it is molten to obtain bark
Liquid, wherein the frequency of microwave heating is 400~800MHz；
3）The swelling of bark activates：Solid sodium hydroxide activation swelling is added in bark solution；
4）Vacuum distillation：By the bark solution vacuum distillation after swelling, colloidal cellulose, i.e. bark ion colloidal sol are obtained.
2. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 1, feature exist
In：Step 1）In, the cleaning method of bark is：After bark is rinsed with clear water, it is put into 30~60min of immersion in acetic acid.
3. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 1, feature exist
In：Step 1）In, the partial size of bark fines is less than 20 μm.
4. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 1, feature exist
In：Step 2）In, the frequency of microwave heating is 600MHz.
5. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 1, feature exist
In：Step 2）In, the highly polar ionic liquid is 1- butyl -3- methylimidazole villaumite solution.
6. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 5, feature exist
In：In the 1- butyl -3- methylimidazole villaumite solution, the mass percent of water is 2~5%.
7. a kind of preparation method of bark ion colloidal sol for lithium battery recycling according to claim 1, feature exist
In：Step 3）In, the additional amount of sodium hydroxide is that 0.05~0.2g sodium hydroxide is added in every milliliter of bark solution.
8. a kind of bark ion colloidal sol for lithium battery recycling, is characterized in：The described in any item preparation sides of claim 1~7
The preparation-obtained bark ion colloidal sol of method.
9. application of the bark ion colloidal sol according to any one of claims 8 in recycling lithium battery.
10. application of the bark ion colloidal sol according to claim 9 in recycling lithium battery, which is characterized in that recycling lithium
The method of battery is as follows：
A, waste and old lithium ion battery is removed, crushes, obtains positive electrode powder；
B, positive electrode powder is dissolved, obtains positive solution；
C, bark ion colloidal sol is added in positive solution, is warming up to 40~60 DEG C of 30~60min of reaction, filters, obtains filter residue 1
With filtrate 1, filter residue 1 recycles aluminium, nickel and copper, after lye or salting liquid precipitate cobalt is added in filtrate 1, filters, resulting filtrate 2 is
Lithium-containing solution.
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| CN109461984B (en) * | 2018-10-19 | 2022-06-07 | 浙江衡远新能源科技有限公司 | Method for recovering valuable metals in waste lithium ion batteries |
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