CN106898719B - Lithium battery diaphragm and preparation method thereof and the lithium battery for using the diaphragm - Google Patents
Lithium battery diaphragm and preparation method thereof and the lithium battery for using the diaphragm Download PDFInfo
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- CN106898719B CN106898719B CN201710078869.1A CN201710078869A CN106898719B CN 106898719 B CN106898719 B CN 106898719B CN 201710078869 A CN201710078869 A CN 201710078869A CN 106898719 B CN106898719 B CN 106898719B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Lithium battery diaphragm and preparation method thereof and the lithium battery for using the diaphragm, the lithium battery diaphragm includes porous septum matrix and is attached to porous septum matrix surface and is attached to the polymer of porous septum matrix internal surface of hole, and the polymer is the polymer based on catechol group.The cathode of lithium battery is lithium an- ode, the present invention is by being modified lithium battery diaphragm, improve wellability and keeping quality of the adsorptivity and electrolyte between diaphragm and metal lithium electrode in diaphragm, inhibit the formation and growth of Li dendrite, it solves diaphragm and metal lithium electrode suction-operated is not strong, the problem of metal lithium electrode surface localised tension cannot be released effectively to easily form Li dendrite in charge and discharge process, improves safety, coulombic efficiency and the cycle life of lithium battery.
Description
Technical field
The invention belongs to technical field of lithium batteries more particularly to a kind of lithium battery diaphragm and preparation method thereof, and use
The lithium battery of the diaphragm.
Background technique
In recent years, with the fast development of portable electronic device, electric car, power grid energy storage technology, people are to high energy
The demand of metric density, the battery of high security and energy-storage system is more more and more urgent.In commercialized electrochemical energy storage device
In, lithium ion battery becomes the optimal selection of people because energy density is high, has extended cycle life.However, due to by electrode
The limitation of material, the work progress for improving lithium ion battery energy density in recent years are more slow.Graphite is most widely used at present
General lithium ion battery negative material, the theoretical capacity of graphite are only 372mAh/g, have been increasingly difficult to meet people to high energy
The demand of metric density lithium ion battery.Compared to graphite cathode, the theoretical capacity of lithium an- ode is considerably higher, reaches
3860mAh/g reaches -3.040V vs. standard hydrogen electrode, therefore use lithium gold in addition metal lithium electrode has most negative potential
The lithium battery for belonging to cathode is expected to realize large-scale application in next-generation electrochemical energy storage field.
But realize that lithium an- ode substitutes graphite cathode still completely and there are many problem needs to capture, one of them is most important
Research topic be how to inhibit the formation and growth of Li dendrite.Li dendrite is that lithium battery lithium ion in charging restores to be formed
Dendritic metal lithium simple substance.The formation of Li dendrite and growth mainly bring following two to endanger: the first, Li dendrite can pierce through every
Film leads to internal short-circuit of battery, forms serious security risk；The second, the formation and growth of Li dendrite will lead to electrolyte with
Contact area increases between lithium metal, Li dendrite continued propagation, electrolyte last decomposition, causes the coulombic efficiency of lithium battery and follows
Ring service life rapid decay.In order to inhibit the growth of Li dendrite, diaphragm is prevented to be pierced, scientist proposes a variety of solutions, such as
It develops high mechanical strength diaphragm [Nano Letters, 2016,16,2981-2987]；It is made using high-end biology cellulose film
Diaphragm [ACS Energy Letters, 2016,1,633-637].The above method under given conditions can be more efficiently
Inhibit the growth of Li dendrite, but diaphragm complex manufacturing technology, cost is very high, and industry efforts there is no to come out.And only inhibit lithium
The growth of dendrite can not fundamentally solve the problems, such as that Li dendrite is brought, and inhibiting the formation of Li dendrite is even more important research
Direction.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium battery diaphragms modified and preparation method thereof, and use the diaphragm
Lithium battery.
To achieve the goals above, the present invention takes following technical solution:
Lithium battery diaphragm, including porous septum matrix and be attached to porous septum matrix surface and be attached to porous septum
The polymer of matrix internal surface of hole, the polymer are the polymer based on catechol group.
More specifically, the monomer of the polymer has structure shown in general formula 1:
Substituent R in general formula 1 be hydroxy-end capped small molecule chain substituent, mercaptan block small molecule chain substituent,
Amino-terminated small molecule chain substituent, ester terminated small molecule chain substituent, fluorine alkane substitute sealing end small molecule chain take
Any one of Dai Jizhong.
More specifically, the substituent R in general formula 1 has the structure as shown in general formula 2:
R ' in general formula 2 is hydroxyl, mercaptan, amino, ester group, any one in fluorine alkane substitute, 1≤n≤10.
More specifically, polymer chooses the polymer monomer preparation containing a kind of substituent group or chooses at least two and contains
It is prepared by the polymer monomer of different substituents.
More specifically, the porous septum matrix be polyethylene diagrams, polypropylene diaphragm, polyethylene/polypropylene bilayer every
Film, polypropylene, polyethylene/polypropylene three-layer membrane, polyvinylidene fluoride membranes, polyacrylonitrile diaphragm, nonwoven cloth diaphragm, glass
Any one in fibre diaphragm.
More specifically, the porous septum matrix with a thickness of 1 μm~100 μm, be attached to poly- on porous septum matrix
Close object with a thickness of 0.1 μm~50 μm.
The preparation method of lithium battery diaphragm, comprising the following steps:
Porous septum matrix is immersed in the precursor liquid containing the polymer monomer based on catechol group；
After porous septum matrix is taken out, porous septum matrix is cleaned, obtains modified lithium battery after drying at room temperature
Diaphragm.
More specifically, soaking time of the porous membrane matrix in precursor liquid is 24 hours, or by porous septum matrix
Ultrasound or concussion in precursor liquid is immersed in handle 5~10 hours.
More specifically, porous septum matrix is cleaned with deionized water and acetone respectively, in 25 DEG C of vacuum environment
Lower drying 24 hours.
More specifically, polymer monomer the preparation method comprises the following steps: potassium carbonate, catechol, which are dissolved in methylene chloride, obtains solution
Paratoluensulfonyl chloride is dissolved in methylene chloride and obtains solution B by A；Solution B is slowly dropped into solution A, and deionized water is added and washes away
Gains after drying, filtering, being evaporated organic solvent, are dissolved in methylene chloride by inorganic salts, liquid separation, are added three under condition of ice bath
Aluminium chloride is slowly added dropwise by the brominated alkanes at least one of hydroxyl, mercaptan, amino, ester group, fluorine alkane substitute sealing end, and addition is gone
Ionized water washes away inorganic salts, and liquid separation drying, filters, is evaporated organic solvent, and gains are dissolved in methylene chloride, the concentrated sulfuric acid is added
Catalysis reflux is added deionized water and washes away inorganic salts, and liquid separation drying, filters, is evaporated organic solvent.
More specifically, polymer monomer is dissolved in TRIS buffer and methanol 1:1 in mass ratio is configured
Mixed liquor, obtain precursor liquid.
Lithium battery is made of anode pole piece, cathode pole piece and diaphragm, the cathode pole piece be lithium anode, it is described every
Film is lithium battery diaphragm above-mentioned.
From the above technical scheme, the present invention contains adjacent benzene on diaphragm matrix surface and the attachment of diaphragm matrix internal surface of hole
The polymer of diphenol group, is modified diaphragm, due to the high-adhesion of catechol group, diaphragm and metal lithium electrode it
Between adsorptivity enhancing, metal lithium electrode surface tension is released effectively in lithium battery cyclic process, to inhibit lithium branch
Brilliant formation and growth；In addition, the small molecule chain of hydroxy-end capped small molecule chain substituent, mercaptan sealing end in polymer replaces
The small molecule chain that base, amino-terminated small molecule chain substituent, ester terminated small molecule chain substituent, fluorine alkane substitute block
Substituent group has good suction-operated to commercialized carbonates electrolyte or ethers electrolyte, for different electricity
Solution liquid choose the polymer monomer containing suitable substituent prepare polymer, can be improved wellability of the electrolyte in diaphragm and
Keeping quality inhibits the formation and growth of Li dendrite, improves lithium so as to improve the uniformity of the current density distribution of lithium ion mobility
Safety, coulombic efficiency and the cycle life of battery.
Specific embodiment
On cathode of lithium battery surface, Li dendrite will form if the current density of lithium ion mobility is unevenly distributed.Every
The infiltration and keeping quality that adsorptivity between film and metal lithium electrode is poor or electrolyte is in diaphragm are poor, can all lead to lithium ion
The current density of migration is unevenly distributed, and then forms Li dendrite.It has been found that being improved if can be modified to diaphragm
Adsorptivity between diaphragm and metal lithium electrode, while wellability and keeping quality of the electrolyte in diaphragm are improved, will effectively it change
The uniformity of the current density distribution of kind lithium ion mobility, to effectively inhibit the formation and growth of Li dendrite, to building Gao An
Quan Xing, high stability lithium battery system be of great significance.
The present invention is modified diaphragm by the polymer containing catechol group, and the diaphragm merging of lithium battery is contained
In the solution for having catechol group polymer monomer, polymer is formed in membrane surface and internal surface of hole, to improve diaphragm
Adsorptivity between lithium an- ode improves wellability and keeping quality of the electrolyte in diaphragm.Lithium battery of the invention every
Film including porous septum matrix and is attached to porous septum matrix surface and is attached to the poly- of porous septum matrix internal surface of hole
Close object.
Polymer of the invention is the polymer based on catechol group, and polymer monomer has shown in general formula 1
Structure:
Substituent R in general formula 1 be hydroxy-end capped small molecule chain substituent, mercaptan block small molecule chain substituent,
Amino-terminated small molecule chain substituent, ester terminated small molecule chain substituent, fluorine alkane substitute sealing end small molecule chain take
Any one of Dai Jizhong.
Substituent R in general formula 1 has the structure as shown in general formula 2:
R ' in general formula 2 is hydroxyl, mercaptan, amino, ester group, any one in fluorine alkane substitute, 1≤n≤10.
Polymer, which chooses the polymer monomer preparation containing a kind of substituent group or chooses at least two, contains different substitutions
It is prepared by the polymer monomer of base.
Porous septum matrix of the invention can for polyethylene diagrams, polypropylene diaphragm, polyethylene/polypropylene two-layer separator,
Polypropylene, polyethylene/polypropylene three-layer membrane, polyvinylidene fluoride membranes, polyacrylonitrile diaphragm, nonwoven cloth diaphragm, glass fibers
Tie up any one in diaphragm.Porous septum matrix with a thickness of 1 μm~100 μm, the polymerization being attached on porous septum matrix
Object with a thickness of 0.1 μm~50 μm.
The preparation method of lithium battery diaphragm of the present invention, comprising the following steps:
Porous septum matrix is immersed in the precursor liquid containing the polymer monomer based on catechol group；It impregnates
Time takes out after being immersed in precursor liquid ultrasonic or concussion processing 5~10 hours for 24 hours or by porous septum matrix；
After porous septum matrix is taken out, porous septum matrix is cleaned, obtains modified lithium battery after drying at room temperature
Diaphragm.Porous septum matrix can be cleaned with deionized water and acetone respectively when cleaning, done under 25 DEG C of vacuum environment
Dry 24 hours.
Following methods preparation can be used in polymer monomer of the invention: potassium carbonate, catechol being dissolved in methylene chloride and obtained
To solution A, paratoluensulfonyl chloride is dissolved in methylene chloride and obtains solution B；Solution B is slowly dropped into solution A, deionized water is added
Inorganic salts are washed away, gains after drying, filtering, being evaporated organic solvent, are dissolved in methylene chloride by liquid separation, are added under condition of ice bath
Enter alchlor, is slowly added dropwise by the brominated alkanes at least one of hydroxyl, mercaptan, amino, ester group, fluorine alkane substitute sealing end, adds
Enter deionized water and wash away inorganic salts, liquid separation drying, filters, is evaporated organic solvent, and gains are dissolved in methylene chloride, are added dense
Sulfuric acid catalysis reflux is added deionized water and washes away inorganic salts, and liquid separation drying, filters, is evaporated organic solvent, obtains shown in general formula 1
The polymer monomer of structure.
Polymer monomer is dissolved in the mixed liquor of TRIS buffer and methanol 1:1 in mass ratio configuration,
Obtain precursor liquid.
Below by specific embodiment and comparative example, the present invention is further illustrated.It is arrived used in following the description
Reagent, material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available
It obtains, related reagent can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
The polymer monomer of the present embodiment is Hydroxytyrosol, and monomer structure isPrecursor liquid is prepared using the polymer monomer；Polyethylene diagrams are cut into
The rectangle diaphragm matrix of long 97mm, width 47mm, diaphragm matrix is immersed in precursor liquid, and modified lithium electricity is obtained after dry
Pond diaphragm.
It takes aluminium foil to cut the rectangle paillon of growth 95mm, width 40mm, coats cobalt acid lithium, another side weldering in the one side of aluminium foil
Aluminium pole ears are connect, positive plate is made；It takes copper foil to cut the rectangle paillon of growth 79mm, width 45mm, is steamed in the one side vacuum of copper foil
The lithium metal layer of 500nm thickness is plated, another side welds nickel tab, negative electrode tab is made；
Diaphragm, positive plate, negative electrode tab are stacked in order, after being encapsulated with aluminum plastic film, electrolyte is filled and seals, list is made
Piece battery.The electrolyte of the present embodiment is that vinyl carbonate, diethyl carbonate, the methyl ethyl carbonate of 1mol/L lithium hexafluoro phosphate are molten
Liquid, wherein vinyl carbonate, diethyl carbonate, methyl ethyl carbonate mass ratio be 1:1:1.
Comparative example 1
The place different from embodiment 1 of comparative example 1 is that diaphragm used is conventional polyethylene diagrams.
Embodiment 2
The brominated alkanes of the present embodiment are 2- bromine ethyl mercaptan, polymer monomer 3,4- dihydroxy benzenes ethyl mercaptan, monomer knot
Structure isPrecursor liquid is prepared using the polymer monomer；Polypropylene diaphragm is cut out
It is cut into the rectangle diaphragm matrix of long 97mm, width 47mm, diaphragm matrix is immersed in precursor liquid, is obtained after dry modified
Lithium battery diaphragm.
The positive plate of the present embodiment, negative electrode tab are same as Example 1, and electrolyte is the ethylene carbon of 1mol/L lithium hexafluoro phosphate
Acid esters, propylene carbonate, dimethyl carbonate solution, wherein vinyl carbonate, propylene carbonate, dimethyl carbonate mass ratio be
3:1:6。
Comparative example 2
The place different from embodiment 2 of comparative example 2 is that diaphragm used is conventional polypropylene diaphragm.
Embodiment 3
The polymer monomer of the present embodiment is 3,4- dihydroxy-Β-phenylethylamine, and monomer structure isPrecursor liquid is prepared using the polymer monomer；Polyethylene diagrams are cut into
The rectangle diaphragm matrix of long 97mm, width 47mm, diaphragm matrix is immersed in precursor liquid, and modified lithium electricity is obtained after dry
Pond diaphragm.
The positive plate of the present embodiment, negative electrode tab are same as Example 1, and electrolyte is the ethylene carbon of 1mol/L lithium hexafluoro phosphate
Acid esters, dimethyl carbonate solution, wherein vinyl carbonate, dimethyl carbonate mass ratio be 1:2.
Comparative example 3
The place different from embodiment 3 of comparative example 3 is that diaphragm used is unmodified conventional polyvinyl diaphragm.
Embodiment 4
The brominated alkanes of the present embodiment are 1- bromine, 3,3,3- trifluoro propane, polymer monomer 3,4- dihydroxy benzenes trifluoro
Propane, monomer structure arePrecursor liquid is prepared using the polymer monomer；It will
Polyethylene diagrams cut the rectangle diaphragm matrix of growth 97mm, width 47mm, and diaphragm matrix is immersed in precursor liquid, after dry
Obtain modified lithium battery diaphragm.
The positive plate of the present embodiment, negative electrode tab are same as Example 1, and electrolyte is the bis- trifluoromethanesulfonimides of 1mol/L
1,3- dioxolane, 1, the 2- ethylene glycol dimethyl ether solution of lithium, wherein the body of 1,3- dioxolane, 1,2- glycol dimethyl ether
Product is than being 1:1.
Comparative example 4
The place different from embodiment 4 of comparative example 4 is that diaphragm used is unmodified conventional polyvinyl diaphragm.
Battery made from embodiment 1 to 4 and comparative example 1 to 4 is subjected to cycle performance test, test method is marked referring to enterprise
It is quasi-, wherein by the battery of embodiment 1 and comparative example 1 in 0.1mA/cm2Charge and discharge cycles test is carried out under current density, it will be real
The battery of example 2 and comparative example 2 is applied in 0.3mA/cm2Charge and discharge cycles test is carried out under current density, by embodiment 3 and comparative example
3 battery is in 0.5mA/cm2Charge and discharge cycles test is carried out under current density, and the battery of embodiment 4 and comparative example 4 is existed
1.5mA/cm2Charge and discharge cycles test is carried out under current density, test result is as shown in table 1.
Table 1
| Group | Current density (mA cm-2) | Cycle-index |
| Embodiment 1 | 0.1 | > 300 |
| Comparative example 1 | 0.1 | 220 |
| Embodiment 2 | 0.3 | > 270 |
| Comparative example 2 | 0.3 | 110 |
| Embodiment 3 | 0.5 | > 280 |
| Comparative example 3 | 0.5 | 100 |
| Embodiment 4 | 1.5 | > 160 |
| Comparative example 4 | 1.5 | 55 |
By the test result of table 1 it is found that the battery of embodiment 1 is after 300 circle circulations, negative terminal surface goes out without Li dendrite
Existing, the battery of comparative example 1 is after 220 circle circulations, since the growth of Li dendrite causes battery short circuit.The battery of embodiment 2
After 270 circle circulations, negative terminal surface occurs without Li dendrite, and the battery of comparative example 2 is after 110 circle circulations, due to lithium
The growth of dendrite causes battery short circuit.After 280 circle circulations, negative terminal surface occurs the battery of embodiment 3 without Li dendrite, right
The battery of ratio 3 is after 100 circle circulations, since the growth of Li dendrite causes battery short circuit.The battery of embodiment 4 passes through
After 160 circle circulations, negative terminal surface occurs without Li dendrite, and the battery of comparative example 4 is after 55 circle circulations, due to Li dendrite
Growth causes battery short circuit.
The present invention improves the adsorptivity between diaphragm and metal lithium electrode by being modified to lithium battery diaphragm, and
Wellability and keeping quality of the electrolyte in diaphragm are improved, the formation and growth of Li dendrite are inhibited, solves diaphragm and lithium gold
It is not strong to belong to electrode adsorption effect, metal lithium electrode surface localised tension cannot be released effectively easily to form lithium in charge and discharge process
The problem of dendrite, improves safety, coulombic efficiency and the cycle life of lithium battery.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (5)
1. the preparation method of lithium battery diaphragm, which comprises the following steps:
Porous septum matrix is immersed in the precursor liquid containing the polymer monomer based on catechol group；
After porous septum matrix is taken out, porous septum matrix is cleaned, obtains modified lithium battery diaphragm after drying at room temperature；
The polymer monomer the preparation method comprises the following steps: potassium carbonate, catechol, which are dissolved in methylene chloride, obtains solution A, will be to first
Benzene sulfonyl chloride is dissolved in methylene chloride and obtains solution B；Solution B is slowly dropped into solution A, inorganic salts are then washed away, in liquid separation, is done
It is dry, filter, be evaporated organic solvent after, gains are dissolved in methylene chloride, alchlor is added under condition of ice bath, is slowly added dropwise
By at least one for the brominated alkanes that hydroxyl, mercaptan, amino, ester group, fluorine alkane substitute block, inorganic salts are then washed away, are being divided
Gains after drying, filtering, being evaporated organic solvent, are dissolved in methylene chloride by liquid, and sulphuric acid catalysis reflux is added, then washes away
Inorganic salts obtain polymer monomer after liquid separation, drying, filtering, being evaporated organic solvent.
2. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that: porous septum matrix is in precursor liquid
Soaking time be 24 hours, or porous septum matrix is immersed in precursor liquid ultrasound or concussion processing 5~10 hours.
3. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that: use deionized water and acetone pair respectively
Porous septum matrix is cleaned, 24 hours dry under 25 DEG C of vacuum environment.
4. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that: polymer monomer is dissolved in three hydroxyl first
The mixed liquor of base aminomethane buffer solution and methanol 1:1 in mass ratio configuration, obtains precursor liquid.
5. lithium battery is made of anode pole piece, cathode pole piece and diaphragm, the cathode pole piece is lithium anode, and feature exists
In: the diaphragm is made of the preparation method of use lithium battery diaphragm according to any one of claims 1-4.
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| JP5270884B2 (en) * | 2007-09-03 | 2013-08-21 | 大阪瓦斯株式会社 | Dispersant and polylactic acid based composite resin particles containing the dispersant |
| CN104183806A (en) * | 2014-08-13 | 2014-12-03 | 江苏安瑞达新材料有限公司 | Composite lithium battery diaphragm and preparation method thereof |
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| JP5270884B2 (en) * | 2007-09-03 | 2013-08-21 | 大阪瓦斯株式会社 | Dispersant and polylactic acid based composite resin particles containing the dispersant |
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