CN110204308A - Using wormcast as lithium ion battery ceramic material, ceramic diaphragm and its preparation of raw material - Google Patents

Using wormcast as lithium ion battery ceramic material, ceramic diaphragm and its preparation of raw material Download PDF

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Publication number
CN110204308A
CN110204308A CN201910472389.2A CN201910472389A CN110204308A CN 110204308 A CN110204308 A CN 110204308A CN 201910472389 A CN201910472389 A CN 201910472389A CN 110204308 A CN110204308 A CN 110204308A
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diaphragm
wormcast
ceramic
lithium ion
ion battery
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张全生
王振宇
张小展
蒋文苹
孙钰媛
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • 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
    • H01M50/431—Inorganic material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of using wormcast as lithium ion battery ceramic material, ceramic diaphragm and its preparation of raw material, by the cleaning of wormcast raw material, ball milling, calcining, then new ceramic material can be obtained in soda acid cleaning, then by drying, slurrying, the techniques such as be coated and dried novel ceramic diaphragm material be made.Compared with prior art; the present invention has good heat-insulating property by the new ceramic material for obtaining wormcast recycling treatment; the surface for being coated on ceramics can preferably play protective effect to the heat and mechanical performance of diaphragm, can be used for the electrochemical energy storing devices such as lithium ion battery, lithium-ion capacitance.

Description

Using wormcast as the lithium ion battery ceramic material of raw material, ceramic diaphragm and its Preparation
Technical field
The invention belongs to wormcast resource utilizations and ceramic diaphragm preparation technical field, are related to one kind with wormcast for original Lithium ion battery ceramic material, ceramic diaphragm and its preparation of material.
Background technique
As what lithium ion battery used becomes increasingly popular, the requirement for performance of lithium ion battery is also increased accordingly.As The diaphragm of one of layer assembly in the key of lithium ion battery, performance decide the interfacial structure of battery, internal resistance etc., directly affect The security performance of the capacity of battery, circulation and battery.In lithium ion battery, after diaphragm draws electrolyte, it can isolate Positive and negative anodes allow the conduction of lithium ion to prevent short circuit；When overcharging or temperature increases, diaphragm is obstructed by closed pore Electric current conduction, prevents from exploding.The superiority and inferiority of membrane properties decides that capacity, cycle performance, impulse electricity current density of battery etc. close Key characteristic.Thermal contraction performance characterizes an important indicator of membrane properties, while being also a Xiang Chong of relationship battery safety Want performance.
Used lithium ion battery separator is main currently on the market are as follows: polyolefins diaphragm, nonwoven fabric base diaphragm and its Its types of diaphragms.Although polyalkene diaphragm has lot of advantages, their thermal stability and poor mechanical properties.And in battery In making, since external and internal cause, the temperature of battery can be risen, this will cause the contraction of diaphragm, in turn result in short circuit, In turn result on fire or explosion
The problems of organic barrier film is tired out in order to improve the polyolefin such as existing PE, and research staff proposes in organic barrier film The scheme of upper coated ceramic coating.Ceramic coating membrane is using PP, PE or multilayer composite membrane as matrix, and surface coats one layer and receives Meter level aluminum oxide material, is handled by special process and matrix bonding is close.The resistance to of lithium ion battery can be significantly improved High-temperature behavior and safety.Chinese patent ZL201310006942.6 discloses a kind of ceramic diaphragm and its application in the battery And the battery containing the ceramic diaphragm, including diaphragm material substrate, matcoveredn, the protection are coated in diaphragm material substrate surface It is the core-shell structure compound of shell that the main component of layer, which is by core, acrylate based polyalcohol of inorganic matter,.The ceramics of the patent Although diaphragm has preferable chemical property, cost of material is higher, and reproducibility is poor.
Wormcast, the i.e. excreta of earthworm, light, the thin uniform, free from extraneous odour of grain, structure and function are special.In nature Survive a large amount of earthworm in soil.Earthworm belongs to Oligochaeta Opisthopora, and the terrestrial earthworm that the whole world has recorded has 12 sections, and 181 Belong to, about 4,000, what China had recorded there are 9 sections 28 to belong to 306 kinds.In the world with the presence of earthworm in most ecosystem, so Wormcast source is very wide.Wormcast is generally used for preparation agro-ecology medicine fertilizer, and this recycling using measure is worth phase To lower.
Currently, still wormcast be used for lithium ion battery being delivered with the technical literature in ceramic material to see.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind is original with wormcast Lithium ion battery ceramic material, ceramic diaphragm and its preparation of material.It is replaced by using novel, cheap biomaterial wormcast Generation tradition, expensive Al2O3、TiO2Equal materials greatly reduce production cost under the premise of meeting identical function, have High industrial application value.
The purpose of the present invention can be achieved through the following technical solutions:
One of the objects of the present invention is to provide a kind of using wormcast as the system of the lithium ion battery ceramic material of raw material Preparation Method, which is characterized in that after taking ball milling of wormcast, first drying, then high temperature is burnt under inert gas atmosphere, it is cooling Afterwards, clean, secondary ball milling, secondary drying to get arrive purpose product ceramic material.
Further, the detailed process of a ball milling are as follows: D50≤20 μm are milled in ethanol solution.
Further, the detailed process of secondary ball milling are as follows: D50≤1 μm is milled in ethanol system.
Wherein, twice in mechanical milling process, earthworm soil raw material is sufficiently crushed, its particle size is made to meet wanting for ceramic material It asks.
Further, the temperature of first drying and secondary drying is 60~120 DEG C.
Wherein, the moisture and residual ethanol in the sufficiently removal earthworm soil of drying twice.
Further, the process of high-temperature roasting specifically: the first constant temperature 1-2h at 100-200 DEG C, at 300-500 DEG C Constant temperature 1-2h, finally the constant temperature 1-2h at 700-900 DEG C.
Wherein, sufficiently go out at 100-200 DEG C earthworm soil in Free water, earthworm is removed under the conditions of 300-500 DEG C Combination water in soil removes the earthworm soil that partial impurities in earthworm soil are needed at 700-900 DEG C.
Wherein, in conjunction with the thermogravimetric atlas analysis of Fig. 1 it is found that temperature is too low to make residual impurity in earthworm soil.
Further, inert gas is one or both of nitrogen or argon gas.
Further, cleaning process are as follows: pickling several times and alkali are carried out in turn to the wormcast raw material after high-temperature roasting It washes, finally washes with water to neutrality.
Further, acid solution used in acid cleaning process is one of hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid or more Kind, concentration 0.5-2mol/L；
Aqueous slkali used in alkaline cleaning procedure is one or both of sodium hydroxide or potassium hydroxide, concentration 0.5- 2mol/L。
Wherein, pickling, alkali cleaning are to remove residual impurity in earthworm soil.
The second object of the present invention is to provide a kind of lithium ion battery ceramic material, using any of the above-described preparation method It is prepared.
The third object of the present invention is to provide a kind of lithium ion battery ceramic diaphragm, including diaphragm matrix, and applies Overlay on the ceramic coating on diaphragm matrix surface, the ceramic coating include required such as right 7 ceramic material (wormcast), Binder (Kynoar, sodium carboxymethylcellulose etc.), dispersing agent (stearmide) and solvent (N-Methyl pyrrolidone, water Solution etc.), wherein ceramic material, binder, dispersing agent and solvent mass ratio be 8:1:1:10.
Further, when ceramic coating in diaphragm matrix for single side coating when, with a thickness of 1-5 μm；
When ceramic coating is dual coating in diaphragm matrix, it is 2-10 μm that both side surface, which coats overall thickness,.
Further, the binder is PVDF (Kynoar), (carboxymethyl is fine by SBR (butadiene-styrene rubber), CMC-Na Tie up plain sodium), Fluorine containing olefine polymer, PI (polyimides), one of PTFE (polytetrafluoroethylene (PTFE)) or PAA (polyacrylic acid) or It is a variety of.
Further, the ceramic matrix is single layer PP diaphragm, single layer PE diaphragm, bilayer PE/PP diaphragm, bilayer PP/PP Any one of diaphragm, three layers of PP/PE/PP diaphragm, PET diaphragm, PI diaphragm, PMIA diaphragm or PBO diaphragm.The thickness of diaphragm matrix About 5-30 μm of degree.
Further, ceramic coating is coated in diaphragm matrix through processes such as slurrying, coating and dryings, and pulping process is such as Under: binder is put into solvent, until being evenly stirred until bubble-free；Ceramic material and dispersing agent is added, after stirring 1~2h, Vacuumize and stir at low speed 12~for 24 hours until ceramic material is fully dispersed in a solvent.Further, when solvent is organic solvent When, the organic binders such as PVDF can only be selected；When solvent is water, it can choose PVDF, also can choose SBR, CMC-Na etc. Aqueous binders.The purpose that the vacuum stirs at low speed is that make material fully dispersed in a solvent, and eliminates in slurry Bubble.Coating process is as follows: the ceramic slurry charging basket vacuum prepared being stored and is transferred in coating room, painting is placed it in Cloth machine enters in feed bin, and adjustment coating thickness opens coating, then by the drying box of coating machine by the ceramics after coating to requiring The wound collection of membrane coil.Dew point in coating room is arranged at -40 DEG C and hereinafter, coating thickness should be adjusted to slightly larger than specified value, To reduce coating thickness in the tension after blade coating due to water；The temperature of drying box is maintained at 60~80 DEG C, root Drying temperature is reasonably adjusted according to the size and coating thickness of drying cabinet；If the ceramic diaphragm after winding only applies single side, directly Into next step；If needing double spread, need for the ceramic diaphragm after winding to be transferred to the ceramic base of coating machine front end The placement location of film.
Drying process is as follows: the ceramic diaphragm after winding being placed in the vacuum drying oven that can periodically vacuumize, is dried.Periodically It vacuumizes and refers to and vacuumized once every 4~6 hours.Drying temperature range is 60~100 DEG C, and preferable temperature is 80 DEG C；It is dry Dry time range is 6~for 24 hours, drying time is according to the water content test result appropriate adjustment of ceramic diaphragm.
The present invention has good heat-insulating property, coating by the new ceramic material for obtaining wormcast recycling treatment The protective effect to the heat and mechanical performance of diaphragm can be preferably played on the surface of ceramics, can be used for lithium ion battery, lithium The electrochemical energy storing devices such as ion capacitance.
Compared with prior art, the invention has the following advantages that
(1) source of the wormcast as the ceramic coating material of diaphragm for lithium ion battery is used for the first time, and derives from earthworm The performance indicator of the ceramic material of earthworm excrement fully meets the requirement of ceramic diaphragm material；
(2) ceramic coating material of the new material as diaphragm for lithium ion battery is used, with traditional aluminium oxide, dioxy Change the materials such as titanium to compare, it is from a wealth of sources and cheap, it is very perfect substitute products；
(3) its influence meeting in terms of quality for diaphragm or lithium ion battery from the ceramic material of wormcast It is smaller；
(4) since the ceramic material from wormcast has good heat-insulating property, it is coated on the surface of ceramics, it can Preferably play the heat protective effect to diaphragm.
Detailed description of the invention
Fig. 1 is the thermogravimetric map of ceramic raw material used in the present invention；
Fig. 2 is the X-ray diffractogram of ceramic raw material used in the present invention.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to Following embodiments.
In following embodiment, raw material or processing technique unless otherwise instructed, then show be this field conventional city Sell product or Technology development.
Embodiment 1
A kind of novel lithium ion battery separator ceramic material prepared using wormcast as raw material, specific preparation step packet It includes:
After first wormcast raw material are washed with water for several times, d50≤20 μm are milled under ethanol system；
Then, the temperature by the wormcast raw material after ball milling in convection oven with 60 DEG C is dried；
Then, the wormcast after drying is placed in Muffle furnace, is heated up under an inert atmosphere with the heating rate of 5 DEG C/min To 200 DEG C, constant temperature 2h；Then 400 DEG C are warming up to the heating rate of 5 DEG C/min, constant temperature 2h；With the heating rate of 5 DEG C/min 700 DEG C are warming up to, constant temperature 2h；Cooled to room temperature under an inert atmosphere；Wherein, the inert atmosphere is nitrogen；
And then, the wormcast raw material after high-temperature roasting are subjected to 2 pickling/alkali cleanings in turn, pilot process water is clear It is washed till neutrality, then carries out next step；The pickling is hydrochloric acid solution, concentration 0.5mol/L with solution；Alkali cleaning solution For sodium hydroxide solution, concentration 0.5mol/L；
Finally, cleaning to neutral wormcast raw material is milled to d50≤1 μm under ethanol system, by material after ball milling Expect to dry in convection oven with 100 DEG C of temperature, can be obtained lithium ion battery separator ceramic material.In conjunction with Fig. 2 it is found that Obtained ceramic material perfect can substitute the traditional materials such as aluminium oxide, titanium dioxide.
Embodiment 2
A kind of novel lithium ion battery separator ceramic material prepared using wormcast as raw material, specific preparation step packet It includes:
After first wormcast raw material are washed with water for several times, d50≤20 μm are milled under ethanol system；
Then, the temperature by the wormcast raw material after ball milling in convection oven with 100 DEG C is dried；
Then, the wormcast after drying is placed in Muffle furnace, is heated up under an inert atmosphere with the heating rate of 2 DEG C/min To 20000 DEG C, constant temperature 1h；Then 500 DEG C are warming up to the heating rate of 2 DEG C/min, constant temperature 1h；With the heating speed of 2 DEG C/min Rate is warming up to 800 DEG C, constant temperature 1h；Cooled to room temperature under an inert atmosphere；Wherein, the inert atmosphere is argon gas；
And then, the wormcast raw material after high-temperature roasting are subjected to 2 pickling/alkali cleanings in turn, water is clear in pilot process It is washed till neutrality, then carries out next step；Wherein, pickling is sulfuric acid solution, concentration 1mol/L with solution；Alkali cleaning is hydrogen with solution Potassium oxide solution, concentration 1mol/L；
Finally, cleaning to neutral wormcast raw material is milled to d50≤1 μm under ethanol system, then will be after ball milling Material is dried in convection oven with 120 DEG C of temperature, can be obtained lithium ion battery separator ceramic material.
Embodiment 3
A kind of novel lithium ion battery separator ceramic material prepared using wormcast as raw material, specific preparation step packet It includes:
After first wormcast raw material are washed with water for several times, d50≤20 μm are milled under ethanol system；
Then, the temperature by the wormcast raw material after ball milling in convection oven with 120 DEG C is dried；
Then, the wormcast after drying is placed in Muffle furnace, is heated up under an inert atmosphere with the heating rate of 8 DEG C/min To 150 DEG C, constant temperature 2h；Then 400 DEG C are warming up to the heating rate of 8 DEG C/min, constant temperature 2h；With the heating rate of 8 DEG C/min 900 DEG C are warming up to, constant temperature 2h；Cooled to room temperature under an inert atmosphere；Inert atmosphere is nitrogen；
And then, the wormcast raw material after high-temperature roasting are subjected to 2 pickling/alkali cleanings in turn, water is clear in pilot process It is washed till neutrality, then carries out next step；Wherein, pickling is nitric acid solution, concentration 1mol/L with solution；Alkali cleaning is hydrogen with solution Sodium hydroxide solution, concentration 1mol/L；
Finally, cleaning to neutral wormcast raw material is milled to d50≤1 μm under ethanol system, then will be after ball milling Material is dried in convection oven with 120 DEG C of temperature, can be obtained lithium ion battery separator ceramic material.
Embodiment 4
A kind of novel lithium ion battery ceramic diaphragm, the ceramics including diaphragm matrix and coated in diaphragm matrix surface Coating two parts, the diaphragm matrix include single layer PP diaphragm, and thickness is about 5~30 μm.
Ceramic coating includes ceramic material, binder, dispersing agent, the solvent etc. using any preparation in embodiment 1.
The thickness of ceramic coating are as follows: about 1~5 μm when single side applies, about 2~10 microns when two-sided painting.
Binder is PVDF；The effect of dispersing agent is that ceramic particle can play preferably wetting work in pulping process With.
In the present embodiment, binder used respectively PVDF, SBR, CMC-Na, Fluorine containing olefine polymer, PI, PTFE or It is arbitrarily selected in PAA.
Embodiment 5
The present embodiment is the preparation method of the novel lithium ion battery ceramic diaphragm in embodiment 4, including dries, makes The techniques such as starch, be coated and dried.
Stoving process is as follows: ceramic material, binder being put into 120 DEG C of vacuum drying ovens, 2~6h, the baking are dried The length of dry time depends on the circumstances according to material moisture measurement result.
Pulping process is as follows: binder being put into solvent, until being evenly stirred until bubble-free；Ceramic material is added and divides Powder, after stirring 1~2h, vacuumize and stir at low speed 12~for 24 hours until ceramic material is fully dispersed in a solvent.
When solvent is organic solvent, the organic binders such as PVDF can only be selected；When solvent is water, can choose PVDF also can choose the aqueous binders such as SBR, CMC-Na.
The purpose that vacuum stirs at low speed is that make material fully dispersed in a solvent, and eliminates the bubble in slurry.
Coating process is as follows: the slurry charging basket vacuum prepared being stored and is transferred in coating room, painting is placed it in Cloth machine enters in feed bin, and adjustment coating thickness opens coating, then by the drying box of coating machine by the ceramics after coating to requiring The wound collection of membrane coil.The dew point setting being coated in room is at -40 DEG C and following；The coating thickness should be adjusted to slightly larger than rule Definite value, to reduce coating thickness in the tension after blade coating due to water；The temperature of drying box is maintained at 80 DEG C, root Drying temperature is reasonably adjusted according to the size and coating thickness of drying cabinet；
If the ceramic diaphragm after winding only applies single side, it is directly entered next step；If needing double spread, need by Ceramic diaphragm after winding is transferred to the placement location of the ceramic basement membrane of coating machine front end.
Drying process is as follows: the ceramic diaphragm after winding being placed in the vacuum drying oven that can periodically vacuumize, is dried；Periodically It vacuumizes and refers to and vacuumized once every 5 hours；Drying temperature range is 60~100 DEG C, and preferable temperature is 80 DEG C；When drying Between range be 6~for 24 hours, drying time is according to the water content test result appropriate adjustment of ceramic diaphragm.
Embodiment 6
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment:
The process of high-temperature roasting specifically: first constant temperature 2h, the constant temperature 2h at 500 DEG C, finally in 700 DEG C at 300 DEG C Lower constant temperature 2h.
Embodiment 7
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment:
The process of high-temperature roasting specifically: first constant temperature 1h, the constant temperature 1h at 600 DEG C, finally in 900 DEG C at 400 DEG C Lower constant temperature 1h.
Embodiment 8
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment, the acid solution correspondence of pickling is replaced with Hydrofluoric acid solution.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention Within protection scope.

Claims (10)

1. using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, which is characterized in that take wormcast primary After ball milling, first drying, then high temperature is burnt under inert gas atmosphere, after cooling, cleaning, secondary ball milling, secondary drying to get To purpose product ceramic material.
2. it is according to claim 1 a kind of using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, It is characterized in that, the detailed process of a ball milling are as follows: be milled to D50≤20 μm in ethanol system；
The detailed process of secondary ball milling are as follows: D50≤1 μm is milled in ethanol system；
The temperature of first drying and secondary drying is 60~120 DEG C.
3. it is according to claim 1 a kind of using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, It is characterized in that, the process of high-temperature roasting specifically: the first constant temperature 1-2h at 300-400 DEG C, then at constant temperature 1- at 500-600 DEG C 2h, finally the constant temperature 1-2h at 700-900 DEG C.
4. it is according to claim 1 a kind of using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, It is characterized in that, inert gas is one or both of nitrogen or argon gas.
5. it is according to claim 1 a kind of using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, It is characterized in that, cleaning process are as follows: carry out pickling several times and alkali cleaning in turn to the wormcast raw material after high-temperature roasting, finally It washes with water to neutrality.
6. it is according to claim 5 a kind of using wormcast as the preparation method of the lithium ion battery ceramic material of raw material, It is characterized in that, acid solution used in acid cleaning process is one of hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid or a variety of, concentration For 0.5-2mol/L；
Aqueous slkali used in alkaline cleaning procedure is one or both of sodium hydroxide or potassium hydroxide, concentration 0.5-2mol/ L。
7. a kind of lithium ion battery ceramic material, which is characterized in that using the preparation method as described in claim 1-6 is any It is prepared.
8. a kind of lithium ion battery ceramic diaphragm, which is characterized in that including diaphragm matrix, and be coated in diaphragm matrix surface Ceramic coating, the ceramic coating includes ceramic material, binder, dispersing agent and solvent as claimed in claim 7, In, ceramic material, binder, dispersing agent and solvent mass ratio be 8:1:1:10.
9. lithium ion battery ceramic diaphragm according to claim 8, which is characterized in that when ceramic coating is in diaphragm matrix When the upper coating for single side, with a thickness of 1-5 μm；When ceramic coating is dual coating in diaphragm matrix, both side surface is applied Covering overall thickness is 2-10 μm.
10. lithium ion battery ceramic diaphragm according to claim 8, which is characterized in that the binder be PVDF, One of SBR, CMC-Na, Fluorine containing olefine polymer, PI, PTFE or PAA or a variety of；
The ceramic matrix is single layer PP diaphragm, single layer PE diaphragm, bilayer PE/PP diaphragm, bilayer PP/PP diaphragm, three layers of PP/ Any one of PE/PP diaphragm, PET diaphragm, PI diaphragm, PMIA diaphragm or PBO diaphragm.
CN201910472389.2A 2019-05-31 2019-05-31 Using wormcast as lithium ion battery ceramic material, ceramic diaphragm and its preparation of raw material Pending CN110204308A (en)

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