CN107195905A - A kind of preparation method and application of cladded type fire retardant - Google Patents
A kind of preparation method and application of cladded type fire retardant Download PDFInfo
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- CN107195905A CN107195905A CN201710284827.3A CN201710284827A CN107195905A CN 107195905 A CN107195905 A CN 107195905A CN 201710284827 A CN201710284827 A CN 201710284827A CN 107195905 A CN107195905 A CN 107195905A
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- fire retardant
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/05—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
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a kind of preparation method of cladded type fire retardant, comprise the following steps：1) fire retardant powder is put into porous container, porous container is placed in reative cell, reative cell is vacuumized, nitrogen is replaced at least three times；2) fire retardant powder is fluidized under the atmosphere of nitrogen or argon gas, or by the way that porous container is rotated up into fire retardant powder dispersion effect；3) one layer of organic coating is coated by molecular-layer deposition technique in fire retardant powder surface；4) cladded type fire retardant is produced by atom layer deposition process one layer of inorganic coating of cladding in the fire retardant powder surface for being coated with organic coating.The present invention coats organic coating and inorganic coating on fire-retardant powder surface by molecular-layer deposition and atom layer deposition process, coating effectively isolates the organic electrolyte, positive pole, negative pole of fire retardant and battery, so that fire retardant does not interfere with the chemical property and cycle life of lithium battery.
Description
Technical field
The invention belongs to additives for battery technical field, and in particular to a kind of preparation method of cladded type fire retardant and should
With.
Background technology
Lithium ion battery has the advantages that high-energy-density, high open circuit voltage, memory-less effect, low self-discharge, extensively should
For consumption electronic product, military use product, aeronautical product etc..However, the safety problem of lithium ion battery is its large-scale application
Primary problems faced, especially in terms of electric automobile, hybrid vehicle.Lithium ion battery overcharging, overheat, pierce through,
It can trigger thermal runaway under the conditions of extruding etc., cause burning or even explode.This is due to that current lithium ion battery commonly uses flammable carbon
Acid esters is used as electrolyte.And the existing most economical method for effectively improving lithium ion battery security is to regard fire retardant as addition
Agent or cosolvent are added in electrolyte.
Study more for organic phosphorus flame retardant, organic halogenated flame retardant and composite flame-retardant agent etc. at present, be added into
In conventional electrolysis liquid, inflammable organic electrolyte can be made to become fire retardant or non-ignitable.Such as：KangXu etc. by trimethyl phosphate and
Triethyl phosphate is added to 1.0M LiPF as flame-retardant additive6In-EC+EMC electrolyte, when addition is 40%, electricity
Solution liquid self-extinguishing time (SET) be greatly reduced (XuK, DingMS, ZhangS,
etal.Anattempttoformulatenonflammable
lithiumionelectrolyteswithalkylphosphatesandphosphazenes[J]
.JournaloftheElectrochemical Society,2002,149(5):A622-A626.).H.F.Xiang etc. is by first
Base dimethyl phosphate is added to 1M LiPF as additive6In-EC+DEC electrolyte, when addition is 10%, electrolyte is
Incombustible (XiangHF, XuHY, Wang ZZ, etal.Dimethylmethylphosphonate (DMMP)
asanefficientflameretardantadditiveforthelithium-ionbatteryelectrolytes[J]
.JournalofPowerSources,2007,173(1):562-564.).These phosphoric acid esters have good anti-flammability, but
There is high viscosity mostly, high-solidification point is bad to the compatibility (especially negative pole) of electrode when addition is excessive, capacity attenuation compared with
It hurry up.For example, Chinese patent 200710052150.7 provides a kind of flame-retardant electrolyte additive of high-efficiency low-toxicity, using a kind of or
More than one phosphate (methyl-phosphoric acid dimethyl ester, ethyl phosphonic acid diethylester etc.) of person, can as neat solvent or solvent composition
Effectively to improve the security of lithium ion battery, but it is bad with the compatibility of negative material.
Accordingly, it would be desirable to design a kind of BACN, fire retardant can be prevented effectively from and organic electrolyte, positive pole, negative pole are straight
Contact causes side reaction, meanwhile, it can play good flame retardant effect when catching fire occurs for lithium battery.
The content of the invention
The purpose of the present invention is to overcome existing fire retardant to be easily caused electrolyte viscosity to become big, ionic conductivity reduction, and
The directly contact of fire retardant and organic electrolyte, positive pole, negative pole causes the problem of side reaction influences the cycle life of lithium battery.
Therefore, the invention provides a kind of preparation method of cladded type fire retardant, comprising the following steps：
1) fire retardant powder is put into porous container, porous container is placed in reative cell, reative cell is vacuumized, nitrogen is replaced
At least three times.
2) fire retardant powder is fluidized under the atmosphere of nitrogen or argon gas, fluidized pressure is 1~1000torr, or
By the way that porous container is rotated up into fire retardant powder dispersion effect.
3) one layer of organic coating is coated by molecular-layer deposition technique in fire retardant powder surface.
4) one layer of inorganic coating is coated being coated with the fire retardant powder surface of organic coating by atom layer deposition process,
Produce cladded type fire retardant.
Further, the step 2) in fluidized pressure be 10~100torr.
Further, the step 3) in molecular-layer deposition technique detailed process it is as follows：
(a) species of organic coating is deposited as needed, the first presoma of reaction is selected, and deposition process parameters are set：Deposition
25~400 DEG C of temperature, deposition pressure is 0.01~500torr；
(b) the first precursor vapor is incorporated into reative cell in the case where nitrogen or argon gas are carried, the first precursor vapor chemistry is inhaled
It is attached on fire-retardant powder, the retention time is 10~120 seconds；
(c) with nitrogen or argon gas purging reative cell, the second presoma is incorporated into reative cell in the case where nitrogen or argon gas are carried, the
Two presomas and first forerunner's precursor reactant obtain organic coating, and the reaction time is 10~120 seconds；
(d) with nitrogen or argon gas purging reative cell；
(e) repetitive process (b)~(d), until organic coating thickness needed for depositing to.
Further, the first presoma is Adipoyl Chloride, pyromellitic acid anhydride or different to benzene two in the step (a)
Cyanate.
Further, in the step (c) the second presoma be 1,6- hexamethylene diamines, ethylenediamine, 1,10- diamino decanes,
Or 1,4- dihydroxy -2- butine.
Further, the step 4) in atom layer deposition process detailed process it is as follows：
(a) species of deposition of inorganic coatings as needed, selects the presoma of reaction, sets deposition process parameters：Depositing temperature
For 25~400 DEG C, deposition pressure is 0.01~500torr；
(b) precursor vapor is incorporated into reative cell in the case where nitrogen or argon gas are carried, the retention time is 10~120 seconds；
(c) with nitrogen or argon gas purging reative cell, oxygen source steam is incorporated into reative cell in the case where nitrogen or argon gas are carried, kept
Time is 10~120 seconds；
(d) with nitrogen or argon gas purging reative cell；
(e) repetitive process (b)~(d), until inorganic coating thickness needed for depositing to.
Further, presoma is volatile metal alkylamino salt, Organometallic in the atom layer deposition process
One or more of mixtures in compound, halide, alkoxide, metal p-diketonates complex compound；Metal in the presoma is
One or more in aluminium, hafnium, yttrium, zirconium, titanium, zinc, silicon.
Further, oxygen source steam is water, hydrogen peroxide, oxygen, ozone or elemental oxygen in the atom layer deposition process.
Compared with prior art, beneficial effects of the present invention：
(1) preparation method of this cladded type fire retardant that the present invention is provided fire-retardant powder surface by molecular-layer deposition and
Atom layer deposition process coats organic coating and inorganic coating, and coating uniform is fine and close, and thickness is accurately controlled, and coating is to fire-retardant
The damage of agent powder is small.
(2) the cladded type fire retardant prepared by preparation method of the present invention can be effectively by fire retardant and electricity by coating
The organic electrolyte in pond, positive pole, negative pole isolation, so that fire retardant does not interfere with the cycle life of lithium battery.
(3) present invention is by fire-retardant powder Surface coating organic coating and inorganic coating two layers of coatings, being prevented effectively from
The problem of single coating expanded by heating causes coating breaks down and discharges fire retardant.
The present invention is described in further details below with reference to accompanying drawing.
Brief description of the drawings
Fig. 1 is the lithium battery cycle performance figure for the cladded type fire retardant for being coated with embodiment 1；
Fig. 2 is the charging and discharging lithium battery schematic diagram of the cladded type fire retardant and uncoated fire retardant that are coated with embodiment 1；
Fig. 3 is the lithium battery loop test figure of coating cladded type fire retardant and uncoated fire retardant under the conditions of different multiplying.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is all other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of preparation method of cladded type fire retardant is present embodiments provided, wherein fire-retardant powder is trimethyl phosphate, specifically
Comprise the following steps：
(1) trimethyl phosphate powder is put into a porous container with micropore size；(2) porous container is put into reaction
In room, vacuumize, replace nitrogen three times, reative cell is warming up to 200 DEG C, and reative cell maintains 5torr pressure；(3) rotate many
Pore volume device so that powder is sufficiently mixed in porous container cavity；(4) by the first presoma of molecular-layer deposition
hexanedioyl dichloride（Adipoyl Chloride）In the N of 50sccm flow velocitys2Carry lower pulse and enter reative cell, adsorb in phosphorus
On sour trimethyl powder, until reative cell air pressure reaches 6torr, and kept for 60 seconds, then use 50sccm N2Purge and take away surplus
Remaining hexanedioyl dichloride, N2Flushing times are 30s, same second presoma hexane-1,6-diamine
（1,6- hexamethylene diamines）In 50sccm N2Carrying under pulse enter reative cell until air pressure reach 6torr and keep 60 seconds, and with
The hexanedioyl dichloride reactions on trimethyl phosphate powder have been chemisorbed on, polyamide is generated（Polyamide）,
Time is 60s, then excessive hexane-1, and 6-diamine and accessory substance are by 50sccm N2Purging takes reative cell out of, purges
Time is 30s, and this completes a MLD deposition cycle；(5) repeat step (4) 100 times；(6) by ald
Presoma Zr [N (CH3)2]4In the N of 50sccm flow velocitys2Carry lower pulse and enter reative cell, adsorb in trimethyl phosphate powder
On, until reative cell air pressure reaches 6torr, and kept for 60 seconds, then use 50sccm N2Purge and take away remaining Zr [N
(CH3) 2]4, N2Flushing times are 30s, same H2O steam is in 5Osccm N2Carrying under pulse enter reative cell until air pressure
Reach 6torr and kept for 60 seconds, and with the Zr [N (CH that have been chemisorbed on trimethyl phosphate powder3) 2]4Reaction, generation
ZrO2, the time is 60s, and then excessive water vapour and accessory substance are by 50sccm N2Purging takes reative cell out of, and flushing times are
30s, this completes an ALD deposition cycle；(7) repeat step (6) 100 times, that is, obtain organic and inorganic coating cladding
Trimethyl phosphate.
Cladded type fire retardant made from this implementation is coated in the membrane surface of lithium battery, the cycle performance of its lithium battery is such as
Shown in Fig. 1, as shown in Figure 1, the lithium battery stable circulation of the present embodiment cladded type fire retardant is coated with.Meanwhile, it is coated with cladding
The chemical property of the lithium battery of type fire retardant and uncoated fire retardant is as shown in Fig. 2 as shown in Figure 2, be coated with cladded type resistance
The charging and discharging curve for firing the lithium battery of agent is normal, illustrates that fire retardant does not react with the electrolyte of lithium battery in this implementation, or by
Redox, meanwhile, compared to uncoated fire retardant, the lithium battery of the present embodiment cladded type fire retardant is coated with bigger
Polarization and lower mean voltage.
In addition, the present embodiment cladded type fire retardant and uncoated fire retardant are coated in the membrane surface of lithium battery,
Loop test is carried out under the conditions of obstructed multiplying power (0.1C, 0.25C, 0.5C, 0.75C, 1C, 1.5C, 2C, 3C), its result such as Fig. 3 institutes
Show.As a result show, the present embodiment cladded type fire retardant high rate performance is more excellent.
Embodiment 2：
A kind of preparation method of cladded type fire retardant is present embodiments provided, wherein fire-retardant powder is triphenyl phosphate, specifically
Comprise the following steps：
(1) triphenyl phosphate (TPP) powder is put into a porous container with micropore size；(2) porous container is put into
In reative cell, vacuumize, replace nitrogen three times, reative cell is warming up to 300 DEG C, and reative cell maintains 10torr pressure；(3) adopt
Use nitrogen streaming mode so that powder suspends and is sufficiently mixed in porous container cavity, nitrogen flow rate 5000sccm；(4) will
First presoma furo [3,4-f] [2] benzofuran-1,3,5,7-tetrone of molecular-layer deposition（Pyromellitic Acid two
Acid anhydride）Pulse enters reative cell under stream of nitrogen gas carrying, adsorbs on triphenyl phosphate (TPP) powder, the burst length is 30s,
Then N is used2Purge and take away remaining furo [3,4-f] [2] benzofuran-1,3,5,7-tetrone, N2Flushing times are
60s, same second presoma ethane-1,2-diamine（Ethylenediamine）In 5 sccm N2Carrying under pulse enter reaction
Room, and with furo [3,4-f] [2] benzofuran-1 for being chemisorbed on triphenyl phosphate (TPP) powder, 3,5,7-
Tetrone reacts, generation polyimide (polyimides), and the time is 30s, then excessive ethane-1,2-diamine and
Accessory substance is by N2Purging takes reative cell out of, and flushing times are 5s, and this completes a MLD deposition cycle；(5) repeat step
(4) 1000 times；(6) by the presoma Hf [N (CH of ald3)(C2H5)]4Pulse enters anti-under stream of nitrogen gas carrying
Room is answered, is adsorbed on triphenyl phosphate (TPP) powder, the burst length is 30s, then uses N2Purge and take away remaining Hf [N
(CH3)(C2H5)]4, N2Flushing times are 60s, the O that same ozone generator is produced3In 5 sccm N2Carrying under pulse enter
Enter reative cell, and with the Hf [N (CH that have been chemisorbed on triphenyl phosphate (TPP) powder3)(C2H5) ]4Reaction, generation
HfO2, the time is 30s, then excessive O3And accessory substance is by N2Purging takes reative cell out of, and flushing times are 5s, are thus completed
One ALD deposition cycle；(7) repeat step (6) 1000 times, that is, obtain the triphenyl phosphate of organic and inorganic coating cladding
(TPP)。
Embodiment 3：
A kind of preparation method of cladded type fire retardant is present embodiments provided, wherein fire-retardant powder is Fluoroalkyloxy phosphate,
Specifically include following steps：
(1) Fluoroalkyloxy phosphate powder is put into a porous container with micropore size；(2) porous container is put into instead
Answer in room, vacuumize, replace nitrogen three times, reative cell is warming up to 100 DEG C, and reative cell maintains 100mtorr pressure；(3) adopt
Use nitrogen streaming mode so that powder suspends and is sufficiently mixed in porous container cavity, nitrogen flow rate 1000sccm；(4) will
First presoma furo [3,4-f] [2] benzofuran-1,3,5,7-tetrone of molecular-layer deposition（Pyromellitic Acid two
Acid anhydride）In the N of 15sccm flow velocitys2Carry lower pulse and enter reative cell, adsorb on Fluoroalkyloxy phosphate powder, the burst length is
10s, then uses 1000sccmN2Purge and take away remaining furo [3,4-f] [2] benzofuran-1,3,5,7-tetrone,
N2Flushing times are 10s, same second presoma decane-1,10-diamine（1,10- diamino decanes）In N2Carrying
Lower pulse enters reative cell, and with the furo [3,4-f] [2] that has been chemisorbed on Fluoroalkyloxy phosphate powder
Benzofuran-1,3,5,7-tetrone reactions, generation polyimide-amide（Polyimide-amide）, the time is 20s,
Then excessive decane-1,10-diamine and accessory substance are by N2Purging takes reative cell out of, and flushing times are 60s, thus
Complete a MLD deposition cycle；(5) repeat step (4) 500 times；(6) by the precursor A l (CH of ald3) 3
In the N of 15sccm flow velocitys2Carry lower pulse and enter reative cell, adsorb on Fluoroalkyloxy phosphate powder, the burst length is
10s, then uses 1000sccmN2Purge and take away remaining Al (CH3)3, N2Flushing times are 10s, same H2O2In N2Carrying
Lower pulse enters reative cell, and with the Al (CH that have been chemisorbed on Fluoroalkyloxy phosphate powder3)3Reaction, generates Al2O3, when
Between be 20s, subsequent excessive H2O2And accessory substance is by N2Purging takes reative cell out of, and flushing times are 60s, and this completes one
Individual ALD deposition cycle；(7) repeat step (6) 500 times, that is, obtain the Fluoroalkyloxy phosphate of organic and inorganic coating cladding.
Embodiment 4：
A kind of preparation method of cladded type fire retardant is present embodiments provided, wherein fire-retardant powder is Trimethyl phosphite, tool
Body comprises the following steps：
(1) Trimethyl phosphite powder is put into a porous container with micropore size；(2) porous container is put into reaction
In room, vacuumize, replace nitrogen three times, reative cell is warming up to 400 DEG C, and reative cell maintains 0.01torr pressure；(3) rotate
Porous container so that powder is sufficiently mixed in porous container cavity；(4) by the first presoma 1,4- of molecular-layer deposition
diisocyanatobenzene（PPDI）In the N of 30 sccm flow velocitys2Carrying under pulse enter reative cell, inhale
It is attached on Trimethyl phosphite powder, the burst length is 60s, until air pressure reaches 20 torr, then uses 500sccm N2Purging
And take away remaining 1,4-diisocyanatobenzene 3, N2Flushing times are 90s, same second presoma ethane-1,
2-diamine is in 30 sccm N2Carrying under pulse enter reative cell, and with being chemisorbed on Trimethyl phosphite powder
1,4-diisocyanatobenzene3Reaction, generates polyurea（Polyureas）, the time is 60s, then excessive ethane-
1,2-diamine and accessory substance are by 700sccm N2Purging takes reative cell out of, and flushing times are 45s, and this completes one
MLD deposition cycles；(5) repeat step (4) 10 times；(6) by the presoma TiCl of ald4In the N of 30 sccm flow velocitys2
Carrying under pulse enter reative cell, adsorb on Trimethyl phosphite powder, the burst length is 60s, until air pressure reaches
6torr, then uses 500sccm N2Purge and take away remaining TiCl4, N2Flushing times are 90s, same O3In 30sccm N2
Carrying under pulse enter reative cell, and with the TiCl that has been chemisorbed on Trimethyl phosphite powder4Reaction, generates TiO2,
Time is 60s, then excessive O3And accessory substance is by 700sccm N2Purging takes reative cell out of, and flushing times are 45s, thus
Complete an ALD deposition cycle；(7) repeat step (6) 10 times；Obtain the phosphorous acid front three of organic and inorganic coating cladding
Ester.
Embodiment 5：
A kind of preparation method of cladded type fire retardant is present embodiments provided, wherein fire-retardant powder is p isopropylbenzoic acid phenyl hexichol
Ester, specifically includes following steps：
(1) p isopropylbenzoic acid phenyl diphenyl ester (IPPP) powder is put into a porous container with micropore size；(2) will be porous
Container is put into reative cell, is vacuumized, is replaced nitrogen three times, reative cell is warming up to 200 DEG C, and reative cell maintains 10torr pressure
Power；(3) nitrogen streaming mode, fluidized pressure 500torr are used so that powder suspends in porous container cavity and fully mixed
Close, nitrogen flow rate 10sccm；(4) by the first presoma 1,4-diisocyanatobenzene of molecular-layer deposition（To benzene
Diisocyanate）In the N of 8000sccm flow velocitys2Carrying under pulse enter reative cell, adsorb in p isopropylbenzoic acid phenyl diphenyl ester
(IPPP) on powder, the burst length is 120s, then uses 5000sccmN2Purge and take away remaining 1,4-
diisocyanatobenzene, N2Flushing times are 90s, same second presoma but-2-yne-1,4-diol（1,4- bis-
Hydroxyl -2- butine）In 8000sccm N2Carrying under pulse enter reative cell, and with being chemisorbed on p isopropylbenzoic acid phenyl
Isosorbide-5-Nitrae-diisocyanatobenzene reactions on diphenyl ester (IPPP) powder, generate polyurethane（Polyurethane）, when
Between be 45s, subsequent excessive but-2-yne-1,4-diol and accessory substance are by 8000sccm N2Purging takes reative cell out of, purges
Time is 90s, and this completes a MLD deposition cycle；(5) repeat step (4) 800 times；(6) by ald
Presoma Hf (ONEt2)4With Zr (OC (CH3)3)4N of the arbitrary proportion mixed vapour in 8000sccm flow velocitys2Carrying under pulse enter
Enter reative cell, adsorb on p isopropylbenzoic acid phenyl diphenyl ester (IPPP) powder, the burst length is 120s, then uses 8000sccm
N2Purge and take away remaining Hf (ONEt2)4With Zr (OC (CH3)3)4, N2Flushing times are 90s, same H2O is in 8000sccm
N2Carrying under pulse enter reative cell, and with the Hf that has been chemisorbed on p isopropylbenzoic acid phenyl diphenyl ester (IPPP) powder
(ONEt2)4With Zr (OC (CH3)3)4Reaction, generates HfO2And ZrO2, the time is 45s, then excessive water and accessory substance by
8000sccm N2Purging takes reative cell out of, and flushing times are 90s, and this completes an ALD deposition cycle；(7) repeat to walk
Suddenly (6) 800 times, that is, the p isopropylbenzoic acid phenyl diphenyl ester of organic and inorganic coating cladding is obtained.
In summary, the present invention coats organic coating on fire-retardant powder surface by molecular-layer deposition and atom layer deposition process
And inorganic coating, coating effectively isolates the organic electrolyte, positive pole, negative pole of fire retardant and battery, so that fire retardant is not
The chemical property and cycle life of lithium battery can be influenceed.
It is exemplified as above be only to the present invention for example, do not constitute the limitation to protection scope of the present invention, it is all
It is to be belonged to the same or analogous design of the present invention within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of cladded type fire retardant, it is characterised in that：Comprise the following steps：
1) fire retardant powder is put into porous container, porous container is placed in reative cell, reative cell is vacuumized, nitrogen is replaced
At least three times；
2) fire retardant powder is fluidized under the atmosphere of nitrogen or argon gas, fluidized pressure is 1~1000torr, or is passed through
Porous container is rotated up to fire retardant powder dispersion effect；
3) one layer of organic coating is coated by molecular-layer deposition technique in fire retardant powder surface；
4) produced in the fire retardant powder surface for being coated with organic coating by atom layer deposition process one layer of inorganic coating of cladding
Cladded type fire retardant.
2. the preparation method of cladded type fire retardant as claimed in claim 1, it is characterised in that：The step 2) in fluidized pressure
For 10~100torr.
3. the preparation method of cladded type fire retardant as claimed in claim 1, it is characterised in that：The step 3) in molecular layer sink
The detailed process of product technique is as follows：
(a) species of organic coating is deposited as needed, the first presoma of reaction is selected, and deposition process parameters are set：Deposition
25~400 DEG C of temperature, deposition pressure is 0.01~500torr；
(b) the first precursor vapor is incorporated into reative cell in the case where nitrogen or argon gas are carried, the first precursor vapor chemistry is inhaled
It is attached on fire-retardant powder, the retention time is 10~120 seconds；
(c) with nitrogen or argon gas purging reative cell, the second presoma is incorporated into reative cell in the case where nitrogen or argon gas are carried, the
Two presomas and first forerunner's precursor reactant obtain organic coating, and the reaction time is 10~120 seconds；
(d) with nitrogen or argon gas purging reative cell；
(e) repetitive process (b)~(d), until organic coating thickness needed for depositing to.
4. the preparation method of cladded type fire retardant as claimed in claim 3, it is characterised in that：Before first in the step (a)
Drive body is Adipoyl Chloride, pyromellitic acid anhydride or PPDI.
5. the preparation method of cladded type fire retardant as claimed in claim 4, it is characterised in that：Before second in the step (c)
Drive body is 1,6- hexamethylene diamines, ethylenediamine, 1,10- diamino decanes or 1,4- dihydroxy -2- butine.
6. the preparation method of cladded type fire retardant as claimed in claim 1, it is characterised in that：The step 4) in atomic layer deposition
The detailed process of product technique is as follows：
(a) species of deposition of inorganic coatings as needed, selects the presoma of reaction, sets deposition process parameters：Depositing temperature
For 25~400 DEG C, deposition pressure is 0.01~500torr；
(b) precursor vapor is incorporated into reative cell in the case where nitrogen or argon gas are carried, the retention time is 10~120 seconds；
(c) with nitrogen or argon gas purging reative cell, oxygen source steam is incorporated into reative cell in the case where nitrogen or argon gas are carried, kept
Time is 10~120 seconds；
(d) with nitrogen or argon gas purging reative cell；
(e) repetitive process (b)~(d), until inorganic coating thickness needed for depositing to.
7. the preparation method of cladded type fire retardant as claimed in claim 6, it is characterised in that：In the atom layer deposition process
Presoma is in volatile metal alkylamino salt, metallo-organic compound, halide, alkoxide, metal p-diketonates complex compound
One or more of mixtures；Metal in the presoma is the one or more in aluminium, hafnium, yttrium, zirconium, titanium, zinc, silicon.
8. the preparation method of cladded type fire retardant as claimed in claim 6, it is characterised in that：In the atom layer deposition process
Oxygen source steam is water, hydrogen peroxide, oxygen, ozone or elemental oxygen.
9. the application of cladded type fire retardant prepared by a kind of any one of claim 1~8 preparation method, it is characterised in that：Will bag
Type fire retardant is covered to be added in the positive pole of lithium battery, negative pole；Or by cladded type fire retardant be coated to the positive pole of lithium battery, negative pole,
Membrane surface.
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| CN108666124A (en) * | 2018-04-28 | 2018-10-16 | 东莞市嘉达磁电制品有限公司 | A kind of preliminary filling magnetic system producing sintered Nd-Fe-B rare earth permanent magnet product |
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| CN108907183A (en) * | 2018-08-07 | 2018-11-30 | 武汉艾特米克超能新材料科技有限公司 | A kind of metal-powder of double-coating and its preparation method and application |
| CN108933241A (en) * | 2018-07-09 | 2018-12-04 | 武汉艾特米克超能新材料科技有限公司 | A kind of positive electrode of double-coating and preparation method thereof, positive plate and lithium battery |
| CN108987793A (en) * | 2018-06-26 | 2018-12-11 | 桑顿新能源科技有限公司 | A kind of high security lithium ion battery and preparation method thereof |
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