CN107930595A - A kind of porous modified pericarp gel and preparation method for lithium battery recycling - Google Patents
A kind of porous modified pericarp gel and preparation method for lithium battery recycling Download PDFInfo
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- CN107930595A CN107930595A CN201711154063.2A CN201711154063A CN107930595A CN 107930595 A CN107930595 A CN 107930595A CN 201711154063 A CN201711154063 A CN 201711154063A CN 107930595 A CN107930595 A CN 107930595A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention relates to a kind of porous modified pericarp gel and preparation method 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 porous modified pericarp gel and preparation method for lithium battery recycling.This method comprises the following steps：A, pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, crushes ball milling, obtain just gel；B, first gel is immersed in the water reaction, forms porous gel material；C, functional group's grafting is carried out to porous gel material；D, saponification process；E, filtering, washing, drying, to obtain the final product.The porous modified pericarp gel of the present invention, pericarp is used to be prepared for raw material, its preparation method is simple, it is of low cost, there is good absorption property, the metals such as copper in lithium ion battery solution, nickel, cobalt can be adsorbed, adsorption rate is high, ionic adsorption column can be prepared into, in the recycling of lithium ion battery, being with a wide range of applications.
Description
Technical field
The present invention relates to a kind of porous modified pericarp gel and preparation method for lithium battery recycling, belong to lithium-ion electric
Pond recovery technology field.
Background technology
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
Move and carry out work.In charge and discharge process, Li+Round-trip insertion and deintercalation between two electrodes:During charging, Li+From cathode deintercalation,
Anode is embedded in by electrolyte, anode is in rich lithium state；It is then opposite during electric discharge.Battery generally uses the material containing elemental lithium
It is the representative of modern high performance battery as electrode.
Lithium ion battery since commercialization is realized at the end of the 20th century, with its with energy density is big, light weight, long lifespan and
Many advantages, such as without memory, be widely used in electric bicycle, electric tool, vehicle using motor, golf cart, model plane and play
Field of portable electronic apparatus such as the power battery such as tool, mine lamp field, mobile phone, laptop, camera and electronic
In automobile.The following material also has development space in fields such as mobile communication base station, energy storage devices.
The developing rapidly to generate of lithium battery industry largely scraps battery to be recycled, mishandling that environment and human body can be good for
Kang Zaocheng is seriously endangered, and there are huge problem of resource waste.How metal in cell positive material is effectively recycled
It is the outstanding problem that current whole lithium battery downstream industry work faces.
Patent CN106785159A discloses a kind of recovery method of nickel and cobalt containing anode material of lithium battery.Soaked using lye
Bubble, dissolve positive electrode in aluminium, formed meta-aluminate, alkali embathe after nickel and cobalt containing manganese lithium positive electrode powder add acid and
Reducing agent dissolves nickel cobalt manganese lithium compound, and then spent ion exchange resin absorption nickel cobalt manganese metal ion, is obtained using acid regeneration
The salting liquid of nickel cobalt manganese, the acid salt solution containing lithium after ion exchange resin filtering obtains hydrochlorate through evaporating, concentrating and crystallizing, remaining
Liquid obtains lithium carbonate with carbonate deposition.The comprehensive reutilization method of the nickel and cobalt containing anode material of lithium battery of the invention to give up
Bauxite resource and nickel cobalt manganese lithium are fully used in positive electrode, the yield ＞ 95% of nickel cobalt manganese lithium, and technique is simple, and investment is small,
Cost is low.
Patent CN103035977A discloses a kind of method that lithium is separated and recovered from waste and old lithium ion battery.This method will
Split after waste and old lithium ion battery electric discharge, remove battery case；Battery is crushed；Battery after crushing is used
Inorganic acid and oxidant are leached, and filtering, obtains filtrate；The pH value of filtrate is transferred to more than or equal to 8, is filtered to remove impurity
And precipitation, obtain the recovered liquid containing lithium ion；With the lithium ion in resin adsorption recovered liquid；Desorption is carried out to resin, is obtained
The lithium salts of separation and recovery.The recovery method is simple, efficient, purity is high, and does not pollute.
As it can be seen that above method is using after traditional calcining, soda acid immersion, inhaled using common absorption resin
It is attached, so as to recycle nickel cobalt manganese or lithium metal.There are specific surface area is smaller, adsorbance is not high for common ion exchange resin
Defect, therefore, it is necessary to be modified research to absorption resin.
Patent CN105817195 discloses a kind of method for preparing the lithium adsorption structure with bigger serface, uses gas
Lithium adsorbent prepared by sol deposition method, the aerosol deposition method include：(a) lithium manganese oxide powder is synthesized；And (b) is logical
Aerosol deposition method is crossed by lithium manganese oxide powder coating in stromal surface.Lithium adsorbent is characterized in that using aerosol deposition
Thus method even can also greatly reduce lithium in long-time and return later directly by lithium manganese oxide powder coating in various matrix
The reduction of yield.Lithium adsorbent with bigger serface prepared by the preparation method is characterized in that being easily processed, selectivity
Ground and lithium ion react, and have the adsorption area of bigger, be physically with it is chemically stable, and can reversibly make
With.
The lithium adsorption structure that the above method is prepared, although the ratio surface of adsorbent can be improved to a certain extent
Product, still, its preparation method are complicated, and raw material lithium manganese oxide powder price is higher, causes the cost of the adsorbent higher, can not
It is applied on a large scale in the recycling of lithium ion battery.
The content of the invention
For disadvantages described above, the object of the present invention is to provide a kind of porous modified pericarp gel for lithium battery recycling and
Preparation method.
First technical problem that the present invention solves is to provide a kind of preparation method of porous modified pericarp gel.
The preparation method of the porous modified pericarp gel of the present invention, including the following steps carried out successively：
A, pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, crushes ball milling, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；
B, first gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material；
C, functional group's grafting, the gel after being grafted are carried out to porous gel material；
D, the gel after grafting is subjected to saponification process；
E, filtering, washing, drying, obtain porous modified pericarp gel.
The method of the present invention, uses pericarp as raw material, porous modified pericarp gel is prepared, and is found by studying, should
Gel is available for the copper in selective absorption lithium battery solution, nickel, cobalt etc., suction big compared to traditional adsorption column specific surface area
Attached metal ion transmission speed in gel rubber material is fast, and adsorption capacity is strong.
A steps by pericarp gel primarily to be uniformly wrapped in polyester fiber top layer, in order to realize the purpose, preferably
The mass ratio of pericarp, the polyester fiber of facile hydrolysis and gel adjuvant is 10:5~8:2~4；It is furthermore preferred that pericarp, facile hydrolysis
Polyester fiber and gel adjuvant mass ratio be 10:6:3.
Wherein, pericarp refers to fruit shell or crust, and the pericarp said in living usually is generally referred to as exocarp.Pericarp
The fruit parts formed by tissue differentiation, the development of ovary wall.Common pericarp can realize the object of the invention, it is preferred that institute
Pericarp is stated as at least one of orange peel, apple skin, banana skin, pear skin, pomelo peel, lemon peel.
Polyester fiber is synthetic fibers of the polyester formed as organic dibasic acid and dihydric alcohol polycondensation obtained by through spinning, the Yishui River
The polyester fiber of solution is the polyester fiber that easily hydrolyzes in water, and polyester fiber is not facile hydrolysis under normal conditions, still, existing
There is the polyester fiber that investigated facile hydrolysis in technology, pass through modified polyester fiber facile hydrolysis.Common facile hydrolysis
Polyester fiber be suitable for the present invention.
Preferably, the gel adjuvant be gelatin, carragheen, xanthans, sodium alginate, konjaku flour, in agar extremely
Few one kind.
Ball milling is crushed after pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, is on the one hand to raw material
Crush and reduce its granularity, be on the other hand in order to which the gel in pericarp is exposed, and pericarp gel be uniformly wrapped in poly-
Ester fiber top layer, to carry out follow-up processing.
Ball mill is the key equipment that material is broken and then is crushed.This type ore mill is in its cylinder
It is interior to load a certain number of steel balls as abrasive media.Ball mill is by horizontal cylinder, input and output material hollow shaft and mill first class sections
Composition, cylinder are long cylinder, and abrasive body is housed in cylinder, and cylinder manufactures for steel plate, has steel liner plate to be fixed with cylinder, abrasive body
Generally steel ball, and be fitted into by different-diameter and certain proportion in cylinder, abrasive body can also use steel section.The present invention is to ball mill
There is no special requirement, ball mill commonly used in the art can be used.
First gel is immersed in the water by b step, due to the facile hydrolysis of polyester fiber so that polyester fiber is in gel layer internal layer
Hydrolysis, so as to form porous gel material.In theory, it is only necessary to which polyester fiber hydrolysis can reach to the mesh of the present invention
's.In order to improve hydrolysis rate, it is preferred that can suitably heat up during hydrolysis, for example be hydrolyzed at 40~60 DEG C.
In step c, in order to improve adsorption capacity, porous gel material function dough is subjected to, to improve inside gel
Active functional group content.Preferably, the functional group is carboxyl, hydroxyl or amino；More preferably described functional group is carboxyl.
The common method being grafted to functional group in material is suitable for the present invention.It is preferred that use chemical graft method.
Chemical graft method is that chemistry occurs with the monomer or macromolecular chain being grafted using the reactive group of material surface
React and realize surface grafting, including graft, chemistry or ozone initiation grafting.Wherein, graft refers to what is be grafted
The reaction carried out between group on polymer reaction group and graft polymer can be coupled by certain material to realize.Change
Learning initiation grafting is reacted by chemical reagent and Polymer Surface component, activated centre is produced, so as to trigger monomer
Polymerization.And the method that the present invention mainly uses graft.
Preferably, the grafting method is：Silane coupling agent with functional group is dissolved in ethanol, then by porous gel material
Material is put into wherein, 30~60min of supercritical carbon dioxide treatment under the pressure of 10~20MPa, and treatment temperature is 30~50 DEG C.
Preferably, the supercritical carbon dioxide treatment 40min under the pressure of 15MPa, treatment temperature are 40 DEG C.
Wherein, silane coupling agent is a kind of organosilicon compound at the same time containing two kinds of different chemical property groups in the molecule
Thing, its classical product can use general formula YSiX3Represent.Due to the particularity of structure, there is energy and inanimate matter at the same time in the molecule thereof
Material（Such as glass, silica sand, metal）Chemically combined reactive group and with organic material（Synthetic resin etc.）Chemical bond
Reactive group, be usually used in being surface-treated.The silane coupling agent of band functional group in the present invention can be carboxy-silane（Band carboxyl
Silane coupling agent）, silicol（Hydroxyl silane coupling agent）Or amino silane（Silane coupling agent with amino）Deng.
Above-mentioned silane coupling agent can use commercially available.
In Step d, saponification process is carried out, primarily to the specific surface area of porous modified pericarp gel is further improved,
The functional group of activating surface at the same time, improves the absorption property of gel rubber material.Preferably, the saponification process uses strong base solution,
The temperature of saponification process is 30~50 DEG C, and the time is 4~8h.It is furthermore preferred that the temperature of saponification process is 40 DEG C, time 6h.
Strong base solution commonly used in the art is used equally for saponification process, it is preferred that the strong base solution is molten for sodium hydroxide
Liquid.
Second technical problem that the present invention solves is to provide a kind of porous modified pericarp gel.
The porous modified pericarp gel of the present invention, uses pericarp to be prepared for raw material with the method for above-mentioned record, its cost
It is relatively low, and there is good absorption property, copper in lithium ion battery solution, nickel, cobalt etc. can be adsorbed, available for lithium-ion electric
In the recycling of pond positive electrode.
It is the ionic adsorption column that main component is prepared the present invention also provides the porous modified pericarp gel of the present invention.
The ionic adsorption column of the present invention, uses the porous modified pericarp gel of the present invention to pass through conventional suction for main component
The preparation method of attached column is prepared.Small sorption channel after being decomposed inside the ionic adsorption column there are a large amount of polyester fibers,
Bigger than traditional adsorption column specific surface area, the transmission speed of the metal ion of absorption in gel rubber material is fast, and adsorption capacity is strong, tool
There is great practical value.
The present invention also provides application of the porous modified pericarp gel of the present invention in lithium ion battery is recycled.
The porous modified pericarp gel of the present invention, is used directly for the recycling of lithium ion battery, can also be prepared into ion
Adsorption column, in the recycling of lithium ion battery, is adsorbed for the copper in lithium battery solution, nickel, making choice property of cobalt.
Compared with prior art, the present invention has the advantages that：
1）The porous modified pericarp gel of the present invention, it is of low cost, there is good absorption property, lithium ion battery can be adsorbed
The metals such as copper, nickel, cobalt in solution, adsorption rate are high.
2）The porous modified pericarp gel of the present invention, uses pericarp to be prepared for raw material, and its preparation method is simple, prepares
Equipment special Shi Wuxu, manufacturing cost are relatively low.
3）The porous modified pericarp gel of the present invention, can be prepared into ionic adsorption column, compared to traditional ionic adsorption column
For, specific surface area is big, and the transmission speed of the metal ion of absorption in gel rubber material is fast, and adsorption capacity is strong, has great
Practical value.
4）The porous modified pericarp gel of the present invention, available for time in the recycling of lithium ion battery, being lithium ion battery
Receipts provide a new approach, are with a wide range of applications.
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
Scope be only limitted to following example.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
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is orange peel；The gel adjuvant is gelatin；And pericarp, the Yishui River
The polyester fiber of solution and the weight ratio of gel adjuvant are 10:6:3.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Carboxyl functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Silane coupling agent with carboxyl is dissolved in ethanol, then porous gel material is put into wherein, it is overcritical under the pressure of 15MPa
Carbon dioxide treatment 40min, treatment temperature are 40 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 40 DEG C, when
Between be 6h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, it is molten to the nickel ion that ion concentration is 0.01mol/L
Liquid is adsorbed, and by analyzing the ion concentration in absorption residual solution, obtains the nickel ion ion balance of the adsorption column
Adsorbance is shown in Table 1.To ion concentration be 0.01mol/L cobalt ions solution adsorb, by absorption residual solution in from
Sub- concentration is analyzed, and the cobalt ions ion balance adsorbance for obtaining the adsorption column is shown in Table 1.It is 0.01mol/L to ion concentration
Copper ion solution adsorbed, by analyzing the ion concentration in absorption residual solution, obtain the copper of the adsorption column from
Quantum balancing ionic adsorption amount is shown in Table 1.
Embodiment 2
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is apple skin；The gel adjuvant is carragheen；And pericarp, easily
The polyester fiber of hydrolysis and the weight ratio of gel adjuvant are 10:5:4.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Hydroxy functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Hydroxyl silane coupling agent is dissolved in ethanol, then porous gel material is put into wherein, it is overcritical under the pressure of 10MPa
Carbon dioxide treatment 60min, treatment temperature are 30 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 30 DEG C, when
Between be 8h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Embodiment 3
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is banana skin；The gel adjuvant is xanthans；And pericarp, easily
The polyester fiber of hydrolysis and the weight ratio of gel adjuvant are 10:8:2.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Amido functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Silane coupling agent with amino is dissolved in ethanol, then porous gel material is put into wherein, it is overcritical under the pressure of 20MPa
Carbon dioxide treatment 30min, treatment temperature are 50 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 50 DEG C, when
Between be 4h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Embodiment 4
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is pear skin；The gel adjuvant is sodium alginate；And pericarp,
The polyester fiber of facile hydrolysis and the weight ratio of gel adjuvant are 10:6:3.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Carboxyl functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Silane coupling agent with carboxyl group is dissolved in ethanol, then porous gel material is put into wherein, surpasses under the pressure of 17MPa and faces
Boundary carbon dioxide treatment 38min, treatment temperature are 40 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 40 DEG C, when
Between be 5h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Embodiment 5
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is pomelo peel；The gel adjuvant is konjaku flour；And pericarp, easily
The polyester fiber of hydrolysis and the weight ratio of gel adjuvant are 10:7:4.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Carboxyl functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Silane coupling agent with carboxyl is dissolved in ethanol, then porous gel material is put into wherein, it is overcritical under the pressure of 15MPa
Carbon dioxide treatment 50min, treatment temperature are 35 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 35 DEG C, when
Between be 7h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Embodiment 6
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is lemon peel；The gel adjuvant is agar；And pericarp, the Yishui River
The polyester fiber of solution and the weight ratio of gel adjuvant are 10:6:3.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material.
3）Carboxyl functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：
Silane coupling agent with carboxyl is dissolved in ethanol, then porous gel material is put into wherein, it is overcritical under the pressure of 15MPa
Carbon dioxide treatment 30min, treatment temperature are 35 DEG C.
4）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 40 DEG C, when
Between be 6h.
5) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Comparative example 1
Porous modified pericarp gel is prepared with the following method：
1）Pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, ball milling is crushed, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；Wherein, the pericarp is orange peel；The gel adjuvant is gelatin；And pericarp, the Yishui River
The polyester fiber of solution and the weight ratio of gel adjuvant are 10:6:3.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material；
3）Gel after grafting is carried out by saponification process using sodium hydroxide solution；The temperature of saponification process is 40 DEG C, and the time is
6h。
4) filter, wash, is dry, obtaining porous modified pericarp gel.
The specific surface area of the porous modified pericarp gel is measured, the result is shown in table 1.
The porous modified pericarp gel is prepared into ionic adsorption column, nickel ion is measured according to the method described in embodiment 1
Ion balance adsorbance, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Comparative example 2
Porous modified pericarp gel is prepared with the following method：
1）The polyester fiber of facile hydrolysis and gel adjuvant are mixed, crush ball milling, pericarp gel is uniformly wrapped in polyester fibre
Dimension table layer, obtains just gel；Wherein, the gel adjuvant is gelatin；The polyester fiber of facile hydrolysis and the weight of gel adjuvant
Amount is than being 6:3.
2）First gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material；
3）Carboxyl functional group grafting, the gel after being grafted are carried out to porous gel material；The method of the grafting is：By band
The silane coupling agent of carboxyl is dissolved in ethanol, then porous gel material is put into wherein, the overcritical dioxy under the pressure of 15MPa
Change carbon processing 40min, treatment temperature is 40 DEG C.
4) filter, wash, is dry, obtaining porous modified gel.
The specific surface area of the porous modified gel is measured, the result is shown in table 1.
The porous modified gel is prepared into ionic adsorption column, according to the method measure nickel ion balance described in embodiment 1
Ionic adsorption amount, cobalt ions ion balance adsorbance, copper ion ion balance adsorbance, the result is shown in table 1.
Table 1
It can be seen from Table 1 that the porous modified pericarp gel that method only using the present invention obtains just has preferable ratio
Surface area and absorption property, lack the performance that the either step of the method for the present invention can influence the gel.
Claims (10)
1. the preparation method of a kind of porous modified pericarp gel for lithium battery recycling, it is characterised in that including carrying out successively
Following steps：
A, pericarp, the polyester fiber of facile hydrolysis and gel adjuvant are mixed, crushes ball milling, pericarp gel is uniformly wrapped in poly-
Ester fiber top layer, obtains just gel；
B, first gel is immersed in the water, makes polyester fiber in gel internal layer hydrolysis, formation porous gel material；
C, functional group's grafting, the gel after being grafted are carried out to porous gel material；
D, the gel after grafting is subjected to saponification process；
E, filtering, washing, drying, obtain porous modified pericarp gel.
2. the preparation method of the porous modified pericarp gel according to claim 1 for lithium battery recycling, its feature exist
In：In a steps, the mass ratio of pericarp, the polyester fiber of facile hydrolysis and gel adjuvant is 10:5~8:2~4.
3. the preparation method of the porous modified pericarp gel according to claim 1 for lithium battery recycling, its feature exist
In：In a steps, the pericarp is at least one of orange peel, apple skin, banana skin, pear skin, pomelo peel, lemon peel；Institute
Gel adjuvant is stated as at least one of gelatin, carragheen, xanthans, sodium alginate, konjaku flour, agar.
4. the preparation method of the porous modified pericarp gel according to claim 1 for lithium battery recycling, its feature exist
In：In step c, the functional group is carboxyl, hydroxyl or amino.
5. the preparation method of the porous modified pericarp gel according to claim 1 for lithium battery recycling, its feature exist
In：In step c, the grafting is：Silane coupling agent with functional group is dissolved in ethanol, then porous gel material is put into it
In, 30~60min of supercritical carbon dioxide treatment under the pressure of 10~20MPa, treatment temperature is 30~50 DEG C.
6. the preparation method of the porous modified pericarp gel according to claim 1 for lithium battery recycling, its feature exist
In：In Step d, the saponification process uses strong base solution, and the temperature of saponification process is 30~50 DEG C, and the time is 4~8h.
7. the preparation method of the porous modified pericarp gel according to claim 6 for lithium battery recycling, its feature exist
In：The strong base solution is sodium hydroxide solution.
8. the porous modified pericarp gel that claim 1~7 any one of them method is prepared.
9. the ionic adsorption column being prepared using the porous modified pericarp gel described in claim 8 as main component.
10. application of the porous modified pericarp gel in lithium ion battery is recycled described in claim 8.
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