CN106848401A - A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte - Google Patents
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte Download PDFInfo
- Publication number
- CN106848401A CN106848401A CN201710019062.0A CN201710019062A CN106848401A CN 106848401 A CN106848401 A CN 106848401A CN 201710019062 A CN201710019062 A CN 201710019062A CN 106848401 A CN106848401 A CN 106848401A
- Authority
- CN
- China
- Prior art keywords
- additive
- high temperature
- ion battery
- lithium ion
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to technical field of lithium-ion battery.The invention discloses a kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, it includes that weighing, component are added and high temperature includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt additive and high temperature block additive certainly from the steps such as additive addition, its raw material is blocked.Preparation method of electrolyte in the present invention is simple, and preparation efficiency is high；Increase the combined additive of ethers and organic ammonium salt in preparation process on the basis of existing additive, form Low ESR, thin and compact SEI films, improve the internal resistance of cell, high rate performance and cryogenic property.Obtained electrolyte of the invention with the addition of high temperature and block additive certainly, improve the security performance of electrolyte, so that the lithium ion battery for assembling can be automatically stopped exothermic reaction at high temperature, it is ensured that the heat that lithium ion battery is produced in use is unlikely to threaten normally using and using safe for lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, more particularly, to a kind of lithium ion battery high temperature from blocking
The preparation method of electrolyte.
Background technology
In recent years, the fast development in the field such as portable type electronic product, electric automobile, energy-accumulating power station, to energy storage skill
Art proposes requirement higher.Lithium ion battery turns into the primary selection in these fields due to its energy density high, and
Its energy density also more and more higher.Along with lithium ion battery energy density more and more higher, the safety problem that it faces is increasingly
Sternness, the terminal for seriously limiting lithium ion battery with high energy density is used.
The safety problem of lithium ion battery is produced mainly due to battery thermal runaway.Inside battery is because abnormal heat production is anti-
Should, cause internal temperature of battery persistently to raise, then trigger more heat production side reactions, cause battery catches fire even to explode, so that
The security of the lives and property of serious threat user.
In order to improve this problem, people improve the security feature of lithium ion battery using various strategies.Can use
Following method, 1, be the heat endurance that barrier film is improved by ceramic coating, it is to avoid cause both positive and negative polarity to connect because of barrier film thermal contraction
Touch, so as to slow down thermal runaway reaction；2nd, the polymer for melting at a certain temperature is coated on barrier film, using melting for polymer
Change, the lithium ion conduction passage between blocking inside battery both positive and negative polarity, so as to avoid the aggravation of battery thermal runaway.
For method 1, it is only capable of improving the heat endurance of barrier film due to the barrier film of coated ceramic, heat production can not be blocked secondary anti-
Should, therefore its improvement is limited.For method 2, although can partly contain the thermal runaway reaction of battery, but due to lithium
Ion battery electrode is generally all porous electrode, and electrolyte is filled in abundant electrode gap；Lithium ion between both positive and negative polarity
Conduction is blocked, but electrode interior active material is still proceeding with the reaction of electrolyte, can further result in heat
Accumulation triggers thermal runaway reaction.Above two processing method the disadvantage is that, it is all that lithium ion battery separator is processed
Or use new material, but its can not completely from the generation of source containment inside lithium ion cell exothermic reaction and continuous worsening,
This exothermic reaction even can be aggravated so that in a certain amount of time, lithium ion battery becomes to be more prone to spontaneous combustion or blast.
It is right as the research for improving lithium ion battery security accordingly, as the electrolyte of inside lithium ion cell Ion transfer medium
As.
The content of the invention
It is simple the invention provides a kind of preparation method to solve the above problems, high temperature from resistance is with the addition of in preparation process
Disconnected additive, can block electrolysis certainly that can suppress the extremely elevated lithium ion battery high temperature of internal temperature of lithium ion battery
The preparation method of liquid.
To realize above mentioned problem, the technical solution adopted by the present invention is as follows：
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, comprises the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.0~1.6mol/
L, the content of vinylene carbonate is 1.0~2.0wt%, and the content of ether additive is 0.1~5wt%, organic ammonium salt additive
It is 0.1~5wt%, the content that high temperature blocks additive certainly is 5~6wt%；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 500~700 mesh from additive is blocked, then the high temperature after crushing is added to from additive is blocked
In mixed liquor obtained in step b, lithium ion battery high temperature is obtained and blocks electrolyte certainly.
Lithium hexafluoro phosphate is all added in prior art and the present invention in lithium-ion battery electrolytes as lithium salts, but hexafluoro
The chemical stability of lithium phosphate is poor, significant decomposition can occur when temperature is more than 55 DEG C and produce phosphorus pentafluoride, hydrogen fluoride etc.
There is fatal destructiveness to electrolyte and electrode material in objectionable impurities, the reason for this is shorter battery；This hair
The bright combined additive for increasing ethers and organic ammonium salt on the basis of existing additive, ether compound can be absorbed in battery
Preferentially there is oxidation Decomposition in micro H2O and HF, additive, very thin SEI films are formed in positive electrode surface, and the film will effectively press down
The further reaction of electrolyte processed and positive pole, is obviously improved positive electrode stability at high temperature, due to organic ammonium salt addition
Agent can suppress the generation of Li2O in film forming procedure, can form low-impedance on negative material surface, thin and compact SEI films, resistance
Only negative material further reacts with electrolyte, by the connection of additive and uses, and is respectively formed on battery plus-negative plate surface low
Resistance SEI films.So as to reduce battery entirety internal resistance and improve the high-temperature storage and cycle performance of battery.Also it is added with the present invention
From additive is blocked, wherein being added with low melting point polymer additive, the additive is uniformly suspended in high temperature under normal circumstances
In electrolyte, after internal temperature of lithium ion battery is raised and after reaching uniform temperature, low melting point polymer can melt, from
And also result in this additive and be melted into flake, or even numerous additive granules fusion, become to increase the internal resistance of cell every
Layer, and then the Ion transfer inside electrolyte is reduced, reduce the calorigenic action of inside battery, it is ensured that using for lithium ion battery is pacified
Entirely.
Preferably, ether additive is the one kind in four polyethylene glycol groups dimethyl ethers or ethylene glycol monobutyl ether, it is organic
Ammonium salt additive is ammonium benzoate or methyl benzoic acid ammonium, and solvent is dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, carbon
The volume ratio of sour propylene ester is 40~45：55~50：2~4：Organic mixed solvent of 2~4 compositions.
Preferably, high temperature is obtained from additive is blocked by the raw material of following weight portion：12~16 parts of polyethylene, conductive agent
8~16 parts, 8~10 parts of binding agent, 2~3 parts of dispersant, 25~35 parts of absolute ethyl alcohol.
Preferably, polyethylene is low density polyethylene (LDPE), its molecular weight is 20000~40000；Conductive agent is conductive stone
One kind in ink, Ketjen black, acetylene black or Graphene or it is many in mixture；Binding agent is ultra-high molecular weight polyethylene and gathers inclined
PVF is by weight 1：2.5~4 are mixed to prepare；Dispersant is in glyceryl tristearate or the double stearoylketene amine of vinyl
Kind.
Acetylene carbon black, Ketjen black, carbon fiber and CNT are all good conductive agents, in the polymer appropriate doping energy
Enough increase the electric conductivity of polymeric blends, wherein using moderate in grain size and uniform acetylene carbon black as additive in the present invention
In conductive agent, harmful effect of the additive to electrolyte conductivity can be enable to be reduced to minimum.
Kynoar and ultra-high molecular weight polyethylene are engaged can strengthen adhesive property, to other groups in additive
After point playing a part of bonding and mixing various raw materials, can uniformly link together.Kynoar also has one simultaneously
Fixed PTC effects, when temperature is raised, resistance increases rapidly, when binding agent is played a part of, can also be in high temperature environments
Protection battery, slows down or organizes inside battery that exothermic reaction occurs；The ultra-high molecular weight polyethylene of addition can be improved simultaneously
The resistance stability of Kynoar, at a normal temperature can be under the cooperation of additive inner conductive agent, by additive pair
The influence of the internal resistance of cell is preferably minimized, and the conductive agent for adding the suitable addition of suitable species in Kynoar in addition can also
The characteristic of its positive temperature coefficient effect is adjusted, the temperature for making its resistance increase sharply meets use demand；Ultra-high molecular weight polyethylene is also
The probability that Kynoar occurs NTC effects in high temperature can be eliminated, it is ensured that lithium ion battery did not occurred thermal response, it is ensured that
Safety during lithium ion battery use.Because electrolysis additive has positive temperature coefficient effect, positive reason in the present invention
Under condition, its electric conductivity for not interfering with negative pole enables to battery normally to run, when inside lithium ion cell because some are former
When being raised because of temperature（When temperature is increased to more than 120 DEG C）, the positive temperature coefficient effect of electrolysis additive plays a role so that
The internal resistance of electrolyte rises rapidly, so as to reduce the electric current of inside lithium ion cell, and then reduces the product of inside lithium ion cell
Thermal response, so as to ensure the safety that lithium ion battery is used.
Preferably, the Kynoar in binding agent before addition through following treatment：First by Kynoar 200~
Toasted 10~40 minutes at 250 DEG C, then in 10~40 DEG C of quenching-in waters；Then by the Kynoar after quenching 1.5~
Polarized 5~20 minutes under 3MV/cm polarized electric fields, be then crushed to 150~200 mesh.
Commercially available Kynoar is typically the Kynoar of alpha-crystal form, and alpha-crystal form Kynoar also generally just
It is suitable, but the Kynoar of alpha-crystal form does not have positive temperature coefficient effect, and the only Kynoar of beta crystal has positive temperature
Degree coefficient effect, therefore Kynoar needed using preceding being pre-processed, will alpha-crystal form Kynoar try one's best it is many
The Kynoar of beta crystal is converted into, the Quenching Treatment after high-temperature process is exactly to realize this purpose；Heat treatment+quenching
Treatment can only make part alpha-crystal form Kynoar occur crystal formation change, while the beta crystal Kynoar for being obtained effect
Fruit and crystallite dimension aspect are poor, it is therefore desirable to which, in addition electric field plan step, the correlation for further improving Kynoar is special
Property.
Preferably, high temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent is added thereto to successively, ultrasonic disperse 10~20 minutes,
Mixing A liquid is obtained；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；
c）Mixing B liquid is added to mixing A liquid, is stirred with 10~15rpm speed while addition, continued again after mixing completely
Stirred 25~30 minutes with 5~10rpm speed, mixed liquor is obtained；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying, be crushed to 500~600 mesh, made
Obtain high temperature and block additive certainly.
Preferably, being heated to 30~40 DEG C in step a and step b, during ultrasonic disperse；In step c, mixing B liquid is 15
It is completely added in~20 minutes in mixing A liquid.
Therefore, the invention has the advantages that：Preparation method of electrolyte in the present invention is simple, and preparation efficiency is high；
Increase the combined additive of ethers and organic ammonium salt in preparation process on the basis of existing additive, Low ESR can be formed
, thin and compact SEI films improve the internal resistance of cell, high rate performance and cryogenic property.Obtained electrolyte of the invention is also added with height
Temperature improves the security performance of electrolyte, while it is also possible that the lithium ion battery for assembling is in high temperature from blocking additive
Exothermic reaction can be automatically stopped down ensures that the heat that produces in use of lithium ion battery is unlikely to threaten lithium ion
The normal of battery is used and uses safety.
Specific embodiment
Technical scheme is further described with reference to specific embodiment.
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Embodiment in invention, all other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, comprises the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.0mol/L, carbonic acid
The content of vinylene is 1.0wt%, and the content of ether additive is 0.1wt%, and organic ammonium salt additive is 0.1wt%, and high temperature is certainly
The content for blocking additive is 5wt%；Ether additive is four polyethylene glycol groups dimethyl ethers, and organic ammonium salt additive is benzene first
Sour ammonium, solvent is dimethyl carbonate, the volume ratio of methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is 40：55：2：2 compositions
Organic mixed solvent；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 500 mesh from additive is blocked, the high temperature after crushing is then added to step b from additive is blocked
In obtained mixed liquor, lithium ion battery high temperature is obtained and blocks electrolyte certainly；
Wherein, high temperature is obtained from additive is blocked by the raw material of following weight portion：12 parts of polyethylene, 8 parts of conductive agent, binding agent 8
Part, 2 parts of dispersant, 25 parts of absolute ethyl alcohol；Polyethylene is low density polyethylene (LDPE), and its molecular weight is 20000；Conductive agent is conductive stone
Ink；Binding agent is ultra-high molecular weight polyethylene and Kynoar by weight 1：2.5 are mixed to prepare；Dispersant is three stearic acid
Glyceride；Kynoar in binding agent is before addition through following treatment：Kynoar is first toasted 10 points at 200 DEG C
Clock, then in 10 DEG C of quenching-in waters, then polarizes 5 minutes the Kynoar after quenching under 1.5MV/cm polarized electric fields,
Then 150 mesh are crushed to；
High temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent are added thereto to successively, ultrasonic disperse 10 minutes is obtained
Mixing A liquid；30 DEG C are heated to during ultrasonic disperse；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；30 DEG C are heated to during ultrasonic disperse；
c）Will mixing B liquid be added to mixing A liquid, while addition with 10rpm speed stir, mixing completely after again continue with
5rpm speed is stirred 25 minutes, and mixed liquor is obtained；Mixing B liquid was completely added in mixing A liquid in 15 minutes；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying is crushed to 500 mesh, high temperature is obtained
From blocking additive.
Embodiment 2
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, comprises the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.2mol/L, carbonic acid
The content of vinylene is 1.3wt%, and the content of ether additive is 2wt%, and organic ammonium salt additive is 2wt%, and high temperature is blocked certainly
The content of additive is 5.5wt%；Ether additive is four polyethylene glycol groups dimethyl ethers, and organic ammonium salt additive is benzoic acid
Ammonium, solvent is dimethyl carbonate, the volume ratio of methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is 42：53：3：3 compositions
Organic mixed solvent；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 550 mesh from additive is blocked, the high temperature after crushing is then added to step b from additive is blocked
In obtained mixed liquor, lithium ion battery high temperature is obtained and blocks electrolyte certainly；
Wherein, high temperature is obtained from additive is blocked by the raw material of following weight portion：14 parts of polyethylene, 10 parts of conductive agent, binding agent 9
Part, 2.5 parts of dispersant, 30 parts of absolute ethyl alcohol；Polyethylene is low density polyethylene (LDPE), and its molecular weight is 25000；Conductive agent is section's qin
It is black；Binding agent is ultra-high molecular weight polyethylene and Kynoar by weight 1：3 are mixed to prepare；Dispersant is that three stearic acid are sweet
Grease；Kynoar in binding agent is before addition through following treatment：Kynoar is first toasted 20 points at 220 DEG C
Clock, then in 20 DEG C of quenching-in waters, then polarizes 10 minutes the Kynoar after quenching, so under 2MV/cm polarized electric fields
After be crushed to 170 mesh；
High temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent are added thereto to successively, ultrasonic disperse 15 minutes is obtained
Mixing A liquid；35 DEG C are heated to during ultrasonic disperse；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；35 DEG C are heated to during ultrasonic disperse；
c）Will mixing B liquid be added to mixing A liquid, while addition with 12rpm speed stir, mixing completely after again continue with
7rpm speed is stirred 27 minutes, and mixed liquor is obtained；Mixing B liquid was completely added in mixing A liquid in 17 minutes；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying is crushed to 530 mesh, high temperature is obtained
From blocking additive.
Embodiment 3
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, comprises the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.4mol/L, carbonic acid
The content of vinylene is 1.7wt%, and the content of ether additive is 4wt%, and organic ammonium salt additive is 4wt%, and high temperature is blocked certainly
The content of additive is 5.5wt%；Ether additive is ethylene glycol monobutyl ether, and organic ammonium salt additive is methyl benzoic acid ammonium, molten
Agent is dimethyl carbonate, the volume ratio of methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is 43：52：3：3 composition it is organic
Mixed solvent；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 650 mesh from additive is blocked, the high temperature after crushing is then added to step b from additive is blocked
In obtained mixed liquor, lithium ion battery high temperature is obtained and blocks electrolyte certainly；
Wherein, high temperature is obtained from additive is blocked by the raw material of following weight portion：14 parts of polyethylene, 13 parts of conductive agent, binding agent 9
Part, 2.5 parts of dispersant, 30 parts of absolute ethyl alcohol；Polyethylene is low density polyethylene (LDPE), and its molecular weight is 35000；Conductive agent is acetylene
It is black；Binding agent is ultra-high molecular weight polyethylene and Kynoar by weight 1：3.5 are mixed to prepare；Dispersant is double vinyl
Stearoylketene amine；Kynoar in binding agent is before addition through following treatment：Kynoar is first toasted 30 at 230 DEG C
Minute, then in 30 DEG C of quenching-in waters, then the Kynoar after quenching is polarized 15 points under 2.5MV/cm polarized electric fields
Clock, is then crushed to 180 mesh；
High temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent are added thereto to successively, ultrasonic disperse 17 minutes is obtained
Mixing A liquid；35 DEG C are heated to during ultrasonic disperse；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；35 DEG C are heated to during ultrasonic disperse；
c）Will mixing B liquid be added to mixing A liquid, while addition with 13rpm speed stir, mixing completely after again continue with
8rpm speed is stirred 28 minutes, and mixed liquor is obtained；Mixing B liquid was completely added in mixing A liquid in 18 minutes；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying is crushed to 570 mesh, high temperature is obtained
From blocking additive.
Embodiment 4
A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte, comprises the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.6mol/L, carbonic acid
The content of vinylene is 2.0wt%, and the content of ether additive is 5wt%, and organic ammonium salt additive is 5wt%, and high temperature is blocked certainly
The content of additive is 6wt%；Ether additive is ethylene glycol monobutyl ether, and organic ammonium salt additive is methyl benzoic acid ammonium, solvent
For the volume ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is 45：50：4：The organic of 4 compositions mixes
Bonding solvent；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 700 mesh from additive is blocked, the high temperature after crushing is then added to step b from additive is blocked
In obtained mixed liquor, lithium ion battery high temperature is obtained and blocks electrolyte certainly；
Wherein, high temperature is obtained from additive is blocked by the raw material of following weight portion：16 parts of polyethylene, 16 parts of conductive agent, binding agent
10 parts, 3 parts of dispersant, 35 parts of absolute ethyl alcohol；Polyethylene is low density polyethylene (LDPE), and its molecular weight is 40000；Conductive agent is graphite
Alkene；Binding agent is ultra-high molecular weight polyethylene and Kynoar by weight 1：4 are mixed to prepare；Dispersant is double hard vinyl
Esteramides；Kynoar in binding agent is before addition through following treatment：Kynoar is first toasted 40 points at 250 DEG C
Clock, then in 40 DEG C of quenching-in waters, then polarizes 20 minutes the Kynoar after quenching, so under 3MV/cm polarized electric fields
After be crushed to 200 mesh；
High temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent are added thereto to successively, ultrasonic disperse 20 minutes is obtained
Mixing A liquid；40 DEG C are heated to during ultrasonic disperse；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；40 DEG C are heated to during ultrasonic disperse；
c）Will mixing B liquid be added to mixing A liquid, while addition with 15rpm speed stir, mixing completely after again continue with
10rpm speed is stirred 30 minutes, and mixed liquor is obtained；Mixing B liquid was completely added in mixing A liquid in 20 minutes；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying is crushed to 600 mesh, high temperature is obtained
From blocking additive.
Lithium ion battery to electrolysis additive in addition above-described embodiment carries out performance test, in internal temperature of battery
When reaching 110~130 DEG C the charging and discharging currents of battery reduce rapidly, or even stop discharge and recharge, it is to avoid lithium ion battery is because holding
There is the accidents such as spontaneous combustion blast in continuous high temperature.Take the battery after test apart, laminar polymeric layer be attached with barrier film and pole piece,
Also with the presence of similar laminar material in electrolyte, illustrate that the high temperature added in lithium-ion battery electrolytes blocks additive certainly
Work.
It should be appreciated that to those skilled in the art, can according to the above description be improved or be become
Change, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (7)
1. a kind of lithium ion battery blocks the preparation method of electrolyte with high temperature certainly, it is characterised in that comprise the following steps：
a）Prepare raw material by following content：Raw material includes that lithium salts, solvent, vinylene carbonate, ether additive, organic ammonium salt add
Plus agent and high temperature block additive certainly；Wherein lithium salts is lithium hexafluoro phosphate, and its concentration in the electrolytic solution is 1.0~1.6mol/
L, the content of vinylene carbonate is 1.0~2.0wt%, and the content of ether additive is 0.1~5wt%, organic ammonium salt additive
It is 0.1~5wt%, the content that high temperature blocks additive certainly is 5~6wt%；
b）Lithium salts, vinylene carbonate, ether additive, organic ammonium salt additive are dissolved into solvent, mixed liquor is obtained；
c）High temperature is crushed to 500~700 mesh from additive is blocked, then the high temperature after crushing is added to from additive is blocked
In mixed liquor obtained in step b, lithium ion battery high temperature is obtained and blocks electrolyte certainly.
2. a kind of lithium ion battery according to claim 1 blocks the preparation method of electrolyte with high temperature certainly, and its feature exists
In：Described ether additive is the one kind in four polyethylene glycol groups dimethyl ethers or ethylene glycol monobutyl ether, organic ammonium salt addition
Agent is ammonium benzoate or methyl benzoic acid ammonium, and solvent is dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester
Volume ratio be 40~45：55~50：2~4：Organic mixed solvent of 2~4 compositions.
3. a kind of lithium ion battery according to claim 1 blocks the preparation method of electrolyte with high temperature certainly, and its feature exists
It is obtained by the raw material of following weight portion from additive is blocked in described high temperature：12~16 parts of low density polyethylene (LDPE), conductive agent 8~
16 parts, 8~10 parts of binding agent, 2~3 parts of dispersant, 25~35 parts of absolute ethyl alcohol.
4. a kind of lithium ion battery according to claim 3 blocks the preparation method of electrolyte with high temperature certainly, and its feature exists
In：Described low density polyethylene (LDPE) is low density polyethylene (LDPE), and its molecular weight is 20000~40000；Conductive agent be electrically conductive graphite,
One kind in Ketjen black, acetylene black or Graphene or it is many in mixture；Binding agent is ultra-high molecular weight polyethylene and gathers inclined fluorine
Ethene is by weight 1：2.5~4 are mixed to prepare；Dispersant is in glyceryl tristearate or the double stearoylketene amine of vinyl
Kind.
5. a kind of lithium ion battery according to claim 4 blocks the preparation method of electrolyte with high temperature certainly, and its feature exists
In：Kynoar in the binding agent is before addition through following treatment：First Kynoar is dried at 200~250 DEG C
It is roasting 10~40 minutes, then in 10~40 DEG C of quenching-in waters；Then the Kynoar after quenching is polarized in 1.5~3MV/cm
Polarized 5~20 minutes under electric field, be then crushed to 150~200 mesh.
6. a kind of lithium ion battery according to claim 3~5 blocks the preparation method of electrolyte, its feature with high temperature certainly
It is that described high temperature is obtained from additive is blocked by following steps：
a）The absolute ethyl alcohol of half in raw material is taken, dispersant and conductive agent is added thereto to successively, ultrasonic disperse 10~20 minutes,
Mixing A liquid is obtained；
b）Low density polyethylene (LDPE) and binding agent, ultrasonic disperse are sequentially added in second half absolute ethyl alcohol until low density polyethylene (LDPE)
It is completely dissolved with binding agent, mixing B liquid is obtained；
c）Mixing B liquid is added to mixing A liquid, is stirred with 10~15rpm speed while addition, continued again after mixing completely
Stirred 25~30 minutes with 5~10rpm speed, mixed liquor is obtained；
d）The absolute ethyl alcohol in mixed liquor is removed, is then dried, the solid that will be obtained after drying, be crushed to 500~600 mesh, made
Obtain high temperature and block additive certainly.
7. a kind of lithium ion battery according to claim 6 blocks the preparation method of electrolyte with high temperature certainly, and its feature exists
In：In the step a and step b, 30~40 DEG C are heated to during ultrasonic disperse；In step c, mixing B liquid is in 15~20 minutes
It is completely added in mixing A liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710019062.0A CN106848401A (en) | 2017-01-11 | 2017-01-11 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710019062.0A CN106848401A (en) | 2017-01-11 | 2017-01-11 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106848401A true CN106848401A (en) | 2017-06-13 |
Family
ID=59118184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710019062.0A Pending CN106848401A (en) | 2017-01-11 | 2017-01-11 | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106848401A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808090A (en) * | 2018-07-16 | 2018-11-13 | 昆山兴能能源科技有限公司 | A kind of lithium battery electrolytes and lithium battery blocked certainly with high security |
| CN110911688A (en) * | 2019-12-16 | 2020-03-24 | 成都爱敏特新能源技术有限公司 | High-safety lithium ion battery cathode composite material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587777A (en) * | 2009-06-19 | 2009-11-25 | 中南大学 | Difunctional electrolyte and preparation method thereof |
| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN102683739A (en) * | 2012-02-20 | 2012-09-19 | 宁德新能源科技有限公司 | Lithium ion battery |
| CN103094578A (en) * | 2013-01-18 | 2013-05-08 | 东莞新能源科技有限公司 | Method for producing flexible package lithium ion battery negative plates |
| CN103367803A (en) * | 2013-06-17 | 2013-10-23 | 杭州力奥科技有限公司 | Lithium iron phosphate battery with lithium ion battery electrolyte suitable for ultralow-temperature charging and discharging |
| CN103500846A (en) * | 2013-10-08 | 2014-01-08 | 无锡华燕新电源有限公司 | Colloid power battery internal formation electrolyte and preparation method thereof |
| WO2014167035A1 (en) * | 2013-04-12 | 2014-10-16 | Lonza Ltd | Method for preparation of fluoro and chloro cyano compounds of the 15th group |
| CN105390737A (en) * | 2015-11-02 | 2016-03-09 | 中国第一汽车股份有限公司 | Lithium ion battery with thermodynamic protection effect |
| CN105788863A (en) * | 2016-02-29 | 2016-07-20 | 杭州电子科技大学 | Preparation method for polyvinylidene fluoride thin film electret |
-
2017
- 2017-01-11 CN CN201710019062.0A patent/CN106848401A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587777A (en) * | 2009-06-19 | 2009-11-25 | 中南大学 | Difunctional electrolyte and preparation method thereof |
| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN102683739A (en) * | 2012-02-20 | 2012-09-19 | 宁德新能源科技有限公司 | Lithium ion battery |
| CN103094578A (en) * | 2013-01-18 | 2013-05-08 | 东莞新能源科技有限公司 | Method for producing flexible package lithium ion battery negative plates |
| WO2014167035A1 (en) * | 2013-04-12 | 2014-10-16 | Lonza Ltd | Method for preparation of fluoro and chloro cyano compounds of the 15th group |
| CN103367803A (en) * | 2013-06-17 | 2013-10-23 | 杭州力奥科技有限公司 | Lithium iron phosphate battery with lithium ion battery electrolyte suitable for ultralow-temperature charging and discharging |
| CN103500846A (en) * | 2013-10-08 | 2014-01-08 | 无锡华燕新电源有限公司 | Colloid power battery internal formation electrolyte and preparation method thereof |
| CN105390737A (en) * | 2015-11-02 | 2016-03-09 | 中国第一汽车股份有限公司 | Lithium ion battery with thermodynamic protection effect |
| CN105788863A (en) * | 2016-02-29 | 2016-07-20 | 杭州电子科技大学 | Preparation method for polyvinylidene fluoride thin film electret |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808090A (en) * | 2018-07-16 | 2018-11-13 | 昆山兴能能源科技有限公司 | A kind of lithium battery electrolytes and lithium battery blocked certainly with high security |
| CN110911688A (en) * | 2019-12-16 | 2020-03-24 | 成都爱敏特新能源技术有限公司 | High-safety lithium ion battery cathode composite material and preparation method thereof |
| CN110911688B (en) * | 2019-12-16 | 2021-04-09 | 成都爱敏特新能源技术有限公司 | High-safety lithium ion battery cathode composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103779607B (en) | A kind of electrolyte and lithium rechargeable battery | |
| CN104269576B (en) | A kind of electrolyte and the lithium ion battery using the electrolyte | |
| CN105489857B (en) | A kind of quick charge lithium ion battery | |
| CN103337631B (en) | Improve lithium titanate high-rate discharge ability and suppress the carbon nitrogen of aerogenesis to be total to method for coating | |
| CN109585921B (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN109346767A (en) | A kind of solid polymer electrolyte and its application in lithium metal battery | |
| CN103151560B (en) | Lithium ion battery electrolyte solution and its additive | |
| CN102496737A (en) | Lithium ion battery electrolyte and lithium ion battery prepared therefrom | |
| CN109244529A (en) | A kind of lithium ion battery high-voltage electrolyte and the lithium ion battery using the electrolyte | |
| CN108808071A (en) | A kind of nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery | |
| CN109546206B (en) | Wide-temperature range type lithium ion battery composite solid electrolyte and preparation method thereof | |
| KR102535068B1 (en) | lithium ion secondary battery | |
| EP3780168B1 (en) | Positive electrode plate, method for preparing the same and lithium-ion secondary battery | |
| WO2016029379A1 (en) | Fluorine-substituted propylene carbonate-based electrolyte and lithium-ion battery | |
| CN107017433A (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN109273767A (en) | A kind of chain fluoro ester type compound and its purposes as lithium-ion battery electrolytes solvent | |
| CN106558702A (en) | A kind of negative electrode for lithium ion battery slurry | |
| CN106675449B (en) | A kind of lithium ion battery high safety negative electrode slurry binding agent | |
| CN106848400A (en) | A kind of highly secure lithium ion battery electrolyte and lithium ion battery | |
| CN115064771A (en) | Sodium ion battery electrolyte, battery and application | |
| CN106848401A (en) | A kind of lithium ion battery high temperature from the preparation method for blocking electrolyte | |
| Wang et al. | In-situ constructing of dual bifunctional interfacial layers of garnet-type Li6. 4La3Zr1. 4Ta0. 6O12 solid electrolyte towards long-cycle stability for flexible solid metal lithium batteries | |
| CN107275672A (en) | It is a kind of containing rubidium and/or the sodium-ion battery electrolysis additive of caesium cation and its application | |
| CN106816631A (en) | A kind of preparation method of electrolyte for lithium ion battery safe additive | |
| CN106848402A (en) | A kind of lithium ion battery high temperature blocks electrolyte certainly |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170613 |
|
| RJ01 | Rejection of invention patent application after publication |