CN110085913A - It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof - Google Patents

It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof Download PDF

Info

Publication number
CN110085913A
CN110085913A CN201910434890.XA CN201910434890A CN110085913A CN 110085913 A CN110085913 A CN 110085913A CN 201910434890 A CN201910434890 A CN 201910434890A CN 110085913 A CN110085913 A CN 110085913A
Authority
CN
China
Prior art keywords
lithium
gross mass
ion battery
electrolyte gross
positive electrode
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
Application number
CN201910434890.XA
Other languages
Chinese (zh)
Inventor
杨书廷
荆汝壹
李娟�
岳红云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Battery Research Institute Co Ltd
Henan Normal University
Original Assignee
Henan Battery Research Institute Co Ltd
Henan Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henan Battery Research Institute Co Ltd, Henan Normal University filed Critical Henan Battery Research Institute Co Ltd
Priority to CN201910434890.XA priority Critical patent/CN110085913A/en
Publication of CN110085913A publication Critical patent/CN110085913A/en
Pending legal-status Critical Current

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
    • H01M10/052—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
    • H01M10/0567—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof, belongs to lithium-ion battery electrolytes technical field.Technical solution of the present invention main points are as follows: lithium-ion battery electrolytes are made of organic solvent, lithium salts and additive, and organic solvent is by carbonic acid lipid solvent group at lithium salts is by lithium hexafluoro phosphate LiPF6It is formed with difluorine oxalic acid boracic acid lithium LiDFOB, additive is by N, N'- sulfuryl diimidazole SDI, fluoro ethylene carbonate FEC and three (trimethyl silane) phosphite ester TMSPi composition.The present invention is during lithium ion battery first charge-discharge, N, and N'- sulfuryl diimidazole SDI and fluoro ethylene carbonate FEC forms good SEI film in cathode, improves the capacity, cycle performance and high temperature shelving performance of battery.N, N'- sulfuryl diimidazole SDI and three (trimethyl silane) phosphite ester TMSPi form one layer of fine and close passivation layer in anode, prevent the dissolution of transition metal in positive electrode, improve the cyclical stability of positive electrode.

Description

It is a kind of to be electrolysed suitable for the lithium ion battery of nickelic positive electrode and silicon-carbon cathode material Liquid and preparation method thereof
Technical field
The invention belongs to lithium-ion battery electrolytes technical fields, and in particular to one kind is suitable for nickelic positive electrode and silicon Lithium-ion battery electrolytes of carbon negative pole material and preparation method thereof.
Background technique
Lithium ion battery because it is high with energy density, power density is high, have extended cycle life, memory-less effect, safety can It leans on and advantages of environment protection, obtains in fields such as portable consumer electronics, electric tool, medical electronics and widely answer With.But the demand recently as its application field to battery energy density rapidly improves, and there is an urgent need to further increase its energy Metric density.
The molar fraction that nickelic positive electrode refers generally to nickel in material is greater than 0.6 nickeliferous positive electrode, such material Have the characteristics that height ratio capacity and low cost, but low there is also capacity retention ratio and the disadvantages of thermal stability is poor.Silica-base material with The silicon carbon material that carbon is compounded to form can reach 380~500mAh/g, be most potential next-generation lithium ion battery negative material One of.But silica-base material, along with serious volume change, leads to charge and discharge during the insertion of lithium ion and abjection Active material in journey in electrode falls off, dusting etc. and influence its cycle life.
Currently used solution mainly has solvent of the exploitation compared with high electrochemical stability window and addition to improve electrolyte The additive of electrochemical stability, to inhibit the interaction of electrolyte and electrode material, or isolation electrolyte and electrode material The direct contact of material.Such as fluorinated ethylene carbonate (FEC), there is good filming performance and oxidative resistance, be added to electrolyte In can be effectively improved cycle performance of battery, but the storage performance of battery and cycle performance are bad under the high temperature conditions.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of lithiums suitable for nickelic positive electrode and silicon-carbon cathode material Ion battery electrolyte and preparation method thereof, the lithium-ion battery electrolytes effectively reduce the internal resistance of battery, improve battery Capacity, while improving the cycle performance and high-temperature storage performance of battery.
The present invention adopts the following technical scheme that one kind is suitable for nickelic positive electrode and silicon-carbon to solve above-mentioned technical problem The lithium-ion battery electrolytes of negative electrode material are made of organic solvent, lithium salts and additive, it is characterised in that: described organic molten Agent is by carbonic acid lipid solvent group at accounting for the 70%~88% of electrolyte gross mass, lithium salts is by lithium hexafluoro phosphate LiPF6With difluoro grass Sour lithium borate LiDFOB composition, accounts for the 11%~14% of electrolyte gross mass, additive is by N, N'- sulfuryl diimidazole SDI, fluoro Ethylene carbonate FEC and three (trimethyl silane) phosphite ester TMSPi composition, accounts for the 1%~16% of electrolyte gross mass.
Preferably, the organic solvent is the mixing of ethylene carbonate EC, methyl ethyl carbonate EMC and dimethyl carbonate DMC Object, the mass ratio of ethylene carbonate EC, methyl ethyl carbonate EMC and dimethyl carbonate DMC are 3:3:4 in the organic solvent.Lithium from The solvent of sub- battery, which generally requires, has the characteristics that high conductivity, low viscosity, high flash point and higher stability, this requires The dielectric constant of solvent is high, and viscosity is small, is commonly at this stage carbonic ester series.
Preferably, the lithium salts is lithium hexafluoro phosphate LiPF6With the mixture of difluorine oxalic acid boracic acid lithium LiDFOB, wherein LiPF610.9%~13%, the LiDFOB for accounting for electrolyte gross mass accounts for the 0.1%~1% of electrolyte gross mass.
Preferably, the lithium salts is lithium hexafluoro phosphate LiPF6With the mixture of difluorine oxalic acid boracic acid lithium LiDFOB, wherein LiPF612.5%, the LiDFOB for accounting for electrolyte gross mass accounts for the 0.5% of electrolyte gross mass.
Preferably, the additive is by N, N'- sulfuryl diimidazole SDI, fluoro ethylene carbonate FEC and three (trimethyl silicanes Alkane) phosphite ester TMSPi composition, wherein N, N'- sulfuryl diimidazole SDI account for the 0.25%~3% of electrolyte gross mass, fluoro carbon Sour ethylene rouge FEC accounts for the 0.5%~10% of electrolyte gross mass, and it is total that three (trimethyl silane) phosphite ester TMSPi account for electrolyte The 0.25%~3% of quality.By the collective effect of three of the above additive, it is effectively improved lithium ion cell positive and cathode table The stability of face film forming, substantially increasing using high-nickel material is that anode and silicon carbon material are steady as the circulation of the lithium ion battery of cathode Qualitative and high-temperature storage performance.
Preferably, the positive electrode of the lithium ion battery includes lithium nickelate, nickel ion doped, nickle cobalt lithium manganate or nickel cobalt aluminium At least one of sour lithium.
Preferably, the mass percentage of silicon is 1%~20% in the negative electrode material of the lithium ion battery, carbons activity The mass percentage of substance is 80%~99%.
Preparation of the present invention suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material Method, it is characterised in that specific steps are as follows: in the glove box full of argon gas, by ethylene carbonate EC, methyl ethyl carbonate EMC and Dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, and it is total that electrolyte is added first into reaction vessel The organic solvent of quality 70%~88%, then be added electrolyte gross mass 0.25%~3% N, N'- sulfuryl diimidazole SDI, The fluorinated ethylene carbonate FEC of electrolyte gross mass 0.5%~10% and three (front threes of electrolyte gross mass 0.25%~3% Base silane) phosphite ester TMSPi, it is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 10.9%~13%6And electrolysis The difluorine oxalic acid boracic acid lithium LiDFOB of liquid gross mass 0.1%~1% is thoroughly mixed and uniformly obtains being suitable for nickelic positive material The lithium-ion battery electrolytes of material and silicon-carbon cathode material.
Compared with the prior art, the invention has the following beneficial effects: during lithium ion battery first charge-discharge, N, N'- sulfuryl diimidazole SDI and fluoro ethylene carbonate FEC form good SEI film in cathode, improve battery capacity, Cycle performance and high temperature shelving performance.N, N'- sulfuryl diimidazole SDI and three (trimethyl silane) phosphite ester TMSPi are in anode One layer of fine and close passivation layer is formed, the dissolution of transition metal in positive electrode is prevented, improves the cyclical stability of positive electrode.
Detailed description of the invention
Fig. 1 is lithium-ion battery electrolytes made from Examples 1 to 7 and comparative example 1~4 for cylindrical lithium ion battery Cycle performance comparison diagram.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Comparative example 1
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 87% is added in device, is then slowly added into the lithium hexafluoro phosphate of electrolyte gross mass 12.5% LiPF6With the difluorine oxalic acid boracic acid lithium LiDFOB of electrolyte gross mass 0.5%, it is thoroughly mixed and uniformly obtains comparative example 1 Lithium-ion battery electrolytes.
Comparative example 2
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 82% is added in device, the fluorinated ethylene carbonate of electrolyte gross mass 5% is then added FEC is finally slowly added to the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the difluoro of electrolyte gross mass 0.5% Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of comparative example 2.
Comparative example 3
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 86% is added in device, three (trimethyl silanes) that electrolyte gross mass 1% is then added are sub- Phosphate TMSPi is finally slowly added to the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With electrolyte gross mass 0.5% difluorine oxalic acid boracic acid lithium LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of comparative example 3.
Comparative example 4
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 81% is added in device, the fluorinated ethylene carbonate FEC of electrolyte gross mass 5% is then added With three (trimethyl silane) phosphite ester TMSPi of electrolyte gross mass 1%, it is eventually adding the six of electrolyte gross mass 12.5% Lithium fluophosphate LiPF6With the difluorine oxalic acid boracic acid lithium LiDFOB of electrolyte gross mass 0.5%, it is thoroughly mixed and uniformly obtains pair The lithium-ion battery electrolytes of ratio 4.
By the lithium-ion battery electrolytes of above-mentioned preparation, being injected separately into positive electrode is LiNi0.6Co0.2Mn0.2O2, cathode Material is in the cylindrical lithium ion battery of Si-C composite material (silicone content 5wt%), lithium ion battery after fluid injection through sealing, It shelves, be melted into, aging, the processes such as partial volume, obtaining that high-nickel material is anode and silicon carbon material is the lithium ion battery of cathode.
Embodiment 1
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 80.5% is added in device, the N of electrolyte gross mass 0.5%, two miaow of N'- sulfonyl is then added Three (trimethyl silane) phosphorous of azoles SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 5% and electrolyte gross mass 1% Acid esters TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the two of electrolyte gross mass 0.5% Fluorine Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 1.
Embodiment 2
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 80% is added in device, the N of electrolyte gross mass 1%, N'- sulfuryl diimidazole is then added Three (trimethyl silane) phosphorous acid of SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 5% and electrolyte gross mass 1% Ester TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the difluoro of electrolyte gross mass 0.5% Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 2.
Embodiment 3
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 79.5% is added in device, the N of electrolyte gross mass 1.5%, two miaow of N'- sulfonyl is then added Three (trimethyl silane) phosphorous of azoles SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 5% and electrolyte gross mass 1% Acid esters TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the two of electrolyte gross mass 0.5% Fluorine Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 3.
Embodiment 4
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 74.5% is added in device, the N of electrolyte gross mass 1.5%, two miaow of N'- sulfonyl is then added Azoles SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 10% and three (trimethyl silanes) of electrolyte gross mass 1% are sub- Phosphate TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With electrolyte gross mass 0.5% Difluorine oxalic acid boracic acid lithium LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 4.
Embodiment 5
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 77.5% is added in device, the N of electrolyte gross mass 1.5%, two miaow of N'- sulfonyl is then added Three (trimethyl silane) phosphorous of azoles SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 7% and electrolyte gross mass 1% Acid esters TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the two of electrolyte gross mass 0.5% Fluorine Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 5.
Embodiment 6
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 78% is added in device, the N of electrolyte gross mass 1.5%, N'- sulfuryl diimidazole is then added Three (trimethyl silane) phosphorous of SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 7% and electrolyte gross mass 0.5% Acid esters TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the two of electrolyte gross mass 0.5% Fluorine Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 6.
Embodiment 7
Electrolyte quota step: in the glove box (O for being full of argon gas2< 2ppm, H2O < 1ppm) in, by ethylene carbonate EC, Methyl ethyl carbonate EMC and dimethyl carbonate DMC carries out being mixed to form organic solvent according to mass ratio 3:3:4, holds first to reaction The organic solvent of electrolyte gross mass 75.5% is added in device, the N of electrolyte gross mass 1.5%, two miaow of N'- sulfonyl is then added Three (trimethyl silane) phosphorous of azoles SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 7% and electrolyte gross mass 3% Acid esters TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 12.5%6With the two of electrolyte gross mass 0.5% Fluorine Lithium bis (oxalate) borate LiDFOB is thoroughly mixed and uniformly obtains the lithium-ion battery electrolytes of embodiment 7.
By the lithium-ion battery electrolytes of above-mentioned preparation, being injected separately into positive electrode is LiNi0.6Co0.2Mn0.2O2, cathode Material is in the cylindrical lithium ion battery of Si-C composite material (silicone content 1wt%~20wt%), and the battery after fluid injection is through sealing Mouthful, shelve, be melted into, aging, the processes such as partial volume, obtain that high-nickel material is anode and silicon carbon material is the lithium ion battery of cathode. Partial volume capacity data is counted in table 1.
Above-mentioned comparative example 1~4 and the resulting lithium ion battery of embodiment 1-7 are subjected to following test:
Internal resistance of cell test: comparative example 1~4 and the resulting lithium ion battery of embodiment 1-7 are surveyed with AC internal Resistance tester The internal resistance of cell is tried, is as a result counted in table 1.
Room temperature 1C loop test: comparative example 1~4 connects battery charging and discharging survey with the resulting lithium ion battery of Examples 1 to 7 Examination instrument is tested.First with 1C constant-current charge to upper limit voltage 4.2V, then 4.2V constant-voltage charge (cut-off current 0.05C) is carried out, 5min is stood, then constant-current discharge to lower voltage limit 3.0V, stands 5min.Charge-discharge test, circulation 500 are carried out by the above work step Week.For 500th week discharge capacity statistics in table 1, cycle performance of battery is shown in Fig. 1.
55 DEG C of high-temperature storage performance tests: comparative example 1~4 connects battery with the resulting lithium ion battery of Examples 1 to 7 and fills Discharge tester with 1C constant-current charge to upper limit voltage 4.2V, then carries out 4.2V constant-voltage charge (cut-off current 0.05C), stands 5min, then constant-current discharge to lower voltage limit 3.0V, stands 5min, then by lithium ion battery with 1C constant-current charge to upper limit voltage 4.2V, then 4.2V constant-voltage charge (cut-off current 0.05C) is carried out, 5min is stood, the discharge capacity before recording battery storage；Electricity Pond is put into the insulating box that temperature is 55 ± 2 DEG C, is shelved 7 days；Lithium ion battery is taken out from insulating box, is stood at room temperature Then 2h stands 5min at room temperature with 1C constant-current discharge to 3.0V, the discharge capacity after recording lithium ion battery storage；Again By lithium ion battery with 1C constant-current charge to upper limit voltage 4.2V, then 4.2V constant-voltage charge (cut-off current 0.05C) is carried out, stood 5min, then constant-current discharge to lower voltage limit 3.0V, stands 5min, the recovery capacity after recording lithium ion battery storage.It calculates The capacity retention ratio of lithium ion battery storage front and back, capacity restoration rate are counted in table 1.
Table 1
The battery testing data of comparative example 1~4 and Examples 1 to 7 can be seen that conventional additives fluoro carbon from table 1 Vinyl acetate FEC and three (trimethyl silane) phosphite ester TMSPi be used alone or be used in combination to the cycle performance of battery and High-temperature storage performance all has a certain upgrade, but increases additive N, can be significantly into one after N '-sulfuryl diimidazole SDI Step promotes the cycle performance and high-temperature storage performance of battery.
The battery testing data of Examples 1 to 3 can be seen that additive N from table 1, and N '-sulfuryl diimidazole SDI is not Have an impact with capacity performance, the internal resistance of cell, normal-temperature circulating performance and high-temperature storage performance of the additional amount to battery, additive amount compared with It promotes the effect of positive and negative anodes film forming stability smaller when few.
The battery testing data of embodiment 3~5 can be seen that additive N, N '-sulfuryl diimidazole SDI and fluorine from table 1 When being used cooperatively for ethylene carbonate FEC as positive film for additive, the usage amount of fluorinated ethylene carbonate FEC also can not mistake Height, fluorinated ethylene carbonate FEC content are more than that 10% internal resistance of cell increase later is more, and high-temperature storage performance is deteriorated.
The battery testing data of embodiment 3~5 can be seen that additive N, N '-sulfuryl diimidazole SDI and three from table 1 When (trimethyl silane) phosphite ester TMSPi is used cooperatively as positive film for additive, three (trimethyl silane) phosphite esters The usage amount of TMSPi also can not be excessively high, and three (trimethyl silane) phosphite ester TMSPi contents are more than after 3%, and the internal resistance of cell increases Big more, cyclical stability is deteriorated within 500 weeks.
In conclusion the present invention being used in combination by three of the above additive, the usage amount of each additive is controlled, it can be with The film forming component and film forming stability for adjusting nickelic anode and silicon-carbon cathode, reach raising battery capacity, reduce the internal resistance of cell, mention The effect of high normal-temperature circulating performance and high-temperature storage performance.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (8)

1. a kind of lithium-ion battery electrolytes suitable for nickelic positive electrode and silicon-carbon cathode material, by organic solvent, lithium salts With additive form, it is characterised in that: the organic solvent by carbonic acid lipid solvent group at, account for electrolyte gross mass 70% ~ 88%, lithium salts is by lithium hexafluoro phosphate LiPF6It is formed with difluorine oxalic acid boracic acid lithium LiDFOB, accounts for the 11% ~ 14% of electrolyte gross mass, Additive is by N, N'- sulfuryl diimidazole SDI, fluoro ethylene carbonate FEC and three (trimethyl silane) phosphite ester TMSPi groups At accounting for the 1% ~ 16% of electrolyte gross mass.
2. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the organic solvent is the mixture of ethylene carbonate EC, methyl ethyl carbonate EMC and dimethyl carbonate DMC, it should The mass ratio of ethylene carbonate EC, methyl ethyl carbonate EMC and dimethyl carbonate DMC are 3:3:4 in organic solvent.
3. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the lithium salts is lithium hexafluoro phosphate LiPF6With the mixture of difluorine oxalic acid boracic acid lithium LiDFOB, wherein LiPF6It accounts for 10.9% ~ 13%, LiDFOB of electrolyte gross mass accounts for the 0.1% ~ 1% of electrolyte gross mass.
4. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the lithium salts is lithium hexafluoro phosphate LiPF6With the mixture of difluorine oxalic acid boracic acid lithium LiDFOB, wherein LiPF6It accounts for 12.5%, LiDFOB of electrolyte gross mass accounts for the 0.5% of electrolyte gross mass.
5. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the additive, by N, N'- sulfuryl diimidazole SDI, fluoro ethylene carbonate FEC and three (trimethyl silanes) are sub- Phosphate TMSPi composition, wherein N, N'- sulfuryl diimidazole SDI account for the 0.25% ~ 3% of electrolyte gross mass, fluoro ethylene carbonate FEC accounts for the 0.5% ~ 10% of electrolyte gross mass, three (trimethyl silane) phosphite ester TMSPi account for electrolyte gross mass 0.25% ~ 3%, by the collective effect of three of the above additive, it is effectively improved the stability of lithium ion cell positive and negative terminal surface film forming, Substantially increasing using high-nickel material is anode and silicon carbon material as the cyclical stability of the lithium ion battery of cathode and high temperature storage Performance.
6. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the positive electrode of the lithium ion battery includes lithium nickelate, nickel ion doped, nickle cobalt lithium manganate or nickel cobalt lithium aluminate At least one of.
7. the lithium-ion battery electrolytes according to claim 1 suitable for nickelic positive electrode and silicon-carbon cathode material, It is characterized by: the mass percentage of silicon is 1% ~ 20% in the negative electrode material of the lithium ion battery, carbons active material Mass percentage is 80% ~ 99%.
8. being suitable for the lithium ion of nickelic positive electrode and silicon-carbon cathode material described in a kind of any one of claim 1 ~ 7 The preparation method of battery electrolyte, it is characterised in that specific steps are as follows: in the glove box full of argon gas, by ethylene carbonate EC, methyl ethyl carbonate EMC and dimethyl carbonate DMC carry out being mixed to form organic solvent according to mass ratio 3:3:4, first to reaction The organic solvent of electrolyte gross mass 70% ~ 88% is added in container, the N of electrolyte gross mass 0.25% ~ 3%, N'- sulphur is then added The three of acyl diimidazole SDI, the fluorinated ethylene carbonate FEC of electrolyte gross mass 0.5% ~ 10% and electrolyte gross mass 0.25% ~ 3% (trimethyl silane) phosphite ester TMSPi is eventually adding the lithium hexafluoro phosphate LiPF of electrolyte gross mass 10.9% ~ 13%6And electricity The difluorine oxalic acid boracic acid lithium LiDFOB for solving liquid gross mass 0.1% ~ 1% is thoroughly mixed and uniformly obtains being suitable for nickelic positive material The lithium-ion battery electrolytes of material and silicon-carbon cathode material.
CN201910434890.XA 2019-05-23 2019-05-23 It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof Pending CN110085913A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910434890.XA CN110085913A (en) 2019-05-23 2019-05-23 It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910434890.XA CN110085913A (en) 2019-05-23 2019-05-23 It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110085913A true CN110085913A (en) 2019-08-02

Family

ID=67421519

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910434890.XA Pending CN110085913A (en) 2019-05-23 2019-05-23 It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110085913A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931873A (en) * 2019-12-11 2020-03-27 中国科学院山西煤炭化学研究所 Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system
CN111446500A (en) * 2020-04-09 2020-07-24 东莞市杉杉电池材料有限公司 Lithium ion battery non-aqueous electrolyte and lithium ion battery
CN111900474A (en) * 2020-07-20 2020-11-06 深圳市研一新材料有限责任公司 Electrolyte for natural graphite cathode lithium ion battery
CN112467203A (en) * 2019-09-09 2021-03-09 东莞市杉杉电池材料有限公司 High-voltage-resistant non-aqueous electrolyte for lithium ion battery and ternary high-voltage lithium ion battery
CN113571774A (en) * 2021-06-30 2021-10-29 厦门海辰新能源科技有限公司 Lithium ion battery
CN113644318A (en) * 2021-09-10 2021-11-12 中国科学院宁波材料技术与工程研究所 Intelligent lithium-separation blocking electrolyte, preparation method thereof and lithium ion battery
CN113690490A (en) * 2021-08-27 2021-11-23 中节能万润股份有限公司 Phosphite lithium ion battery electrolyte additive and application thereof
CN113707943A (en) * 2021-08-25 2021-11-26 中国科学院长春应用化学研究所 Electrolyte and double-ion battery
CN114156534A (en) * 2021-12-08 2022-03-08 九江天赐高新材料有限公司 Electrolyte containing nitrogen heterocyclic compound, preparation method and lithium secondary battery
CN114361596A (en) * 2022-02-14 2022-04-15 费县威尚新能源技术中心 Lithium ion battery electrolyte and lithium ion battery
CN114464883A (en) * 2022-01-13 2022-05-10 珠海冠宇电池股份有限公司 High-voltage electrolyte and battery containing same
WO2023082866A1 (en) * 2021-11-09 2023-05-19 宁德时代新能源科技股份有限公司 Secondary battery, method for preparing secondary battery, battery module, battery pack, and electrical apparatus
CN117638201A (en) * 2024-01-24 2024-03-01 宁德新能源科技有限公司 Lithium ion battery and electronic device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002280063A (en) * 2001-03-15 2002-09-27 Sony Corp Electrolyte and battery
US20160218392A1 (en) * 2015-01-23 2016-07-28 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery employing the organic electrolytic solution
CN106025359A (en) * 2016-07-08 2016-10-12 珠海市赛纬电子材料股份有限公司 Lithium ion power battery non-water electrolyte
CN107275676A (en) * 2017-08-04 2017-10-20 广州天赐高新材料股份有限公司 A kind of electrolyte and silicon substrate lithium secondary battery for silicon substrate lithium secondary battery
CN107768719A (en) * 2017-10-18 2018-03-06 东莞市杉杉电池材料有限公司 A kind of lithium-ion battery electrolytes and lithium ion battery
CN108232292A (en) * 2016-12-15 2018-06-29 东莞东阳光科研发有限公司 A kind of electrolyte for lithium ion battery
CN108258315A (en) * 2018-03-15 2018-07-06 合肥国轩高科动力能源有限公司 A kind of combined electrolytic liquid and the high specific energy silicon substrate lithium ion battery containing the combined electrolytic liquid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002280063A (en) * 2001-03-15 2002-09-27 Sony Corp Electrolyte and battery
US20160218392A1 (en) * 2015-01-23 2016-07-28 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery employing the organic electrolytic solution
CN106025359A (en) * 2016-07-08 2016-10-12 珠海市赛纬电子材料股份有限公司 Lithium ion power battery non-water electrolyte
CN108232292A (en) * 2016-12-15 2018-06-29 东莞东阳光科研发有限公司 A kind of electrolyte for lithium ion battery
CN107275676A (en) * 2017-08-04 2017-10-20 广州天赐高新材料股份有限公司 A kind of electrolyte and silicon substrate lithium secondary battery for silicon substrate lithium secondary battery
CN107768719A (en) * 2017-10-18 2018-03-06 东莞市杉杉电池材料有限公司 A kind of lithium-ion battery electrolytes and lithium ion battery
CN108258315A (en) * 2018-03-15 2018-07-06 合肥国轩高科动力能源有限公司 A kind of combined electrolytic liquid and the high specific energy silicon substrate lithium ion battery containing the combined electrolytic liquid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAIBO RONG等: "A novel imidazole-based electrolyte additive for improved electrochemical performance of high voltage nickel-rich cathode coupled with graphite anode lithium ion battery", 《JOURNAL OF POWER SOURCES》 *
韩占立: "锂离子电池高压电解液成膜添加剂及溶剂的研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112467203A (en) * 2019-09-09 2021-03-09 东莞市杉杉电池材料有限公司 High-voltage-resistant non-aqueous electrolyte for lithium ion battery and ternary high-voltage lithium ion battery
CN110931873A (en) * 2019-12-11 2020-03-27 中国科学院山西煤炭化学研究所 Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system
CN111446500A (en) * 2020-04-09 2020-07-24 东莞市杉杉电池材料有限公司 Lithium ion battery non-aqueous electrolyte and lithium ion battery
CN111900474A (en) * 2020-07-20 2020-11-06 深圳市研一新材料有限责任公司 Electrolyte for natural graphite cathode lithium ion battery
CN113571774B (en) * 2021-06-30 2022-10-14 厦门海辰储能科技股份有限公司 Lithium ion battery
CN113571774A (en) * 2021-06-30 2021-10-29 厦门海辰新能源科技有限公司 Lithium ion battery
CN113707943A (en) * 2021-08-25 2021-11-26 中国科学院长春应用化学研究所 Electrolyte and double-ion battery
CN113690490A (en) * 2021-08-27 2021-11-23 中节能万润股份有限公司 Phosphite lithium ion battery electrolyte additive and application thereof
CN113690490B (en) * 2021-08-27 2022-09-20 中节能万润股份有限公司 Phosphite lithium ion battery electrolyte additive and application thereof
CN113644318A (en) * 2021-09-10 2021-11-12 中国科学院宁波材料技术与工程研究所 Intelligent lithium-separation blocking electrolyte, preparation method thereof and lithium ion battery
WO2023082866A1 (en) * 2021-11-09 2023-05-19 宁德时代新能源科技股份有限公司 Secondary battery, method for preparing secondary battery, battery module, battery pack, and electrical apparatus
CN114156534A (en) * 2021-12-08 2022-03-08 九江天赐高新材料有限公司 Electrolyte containing nitrogen heterocyclic compound, preparation method and lithium secondary battery
CN114464883A (en) * 2022-01-13 2022-05-10 珠海冠宇电池股份有限公司 High-voltage electrolyte and battery containing same
CN114464883B (en) * 2022-01-13 2023-06-30 珠海冠宇电池股份有限公司 High-voltage electrolyte and battery containing same
CN114361596A (en) * 2022-02-14 2022-04-15 费县威尚新能源技术中心 Lithium ion battery electrolyte and lithium ion battery
CN117638201A (en) * 2024-01-24 2024-03-01 宁德新能源科技有限公司 Lithium ion battery and electronic device
CN117638201B (en) * 2024-01-24 2024-04-09 宁德新能源科技有限公司 Lithium ion battery and electronic device

Similar Documents

Publication Publication Date Title
CN110085913A (en) It is a kind of suitable for nickelic positive electrode and the lithium-ion battery electrolytes of silicon-carbon cathode material and preparation method thereof
CN105591158B (en) A kind of tertiary cathode material lithium ion battery and its electrolyte
CN105375066B (en) One kind is applied to silicon-carbon cathode lithium-ion battery electrolytes and silicon-carbon cathode lithium ion battery
CN105742707B (en) A kind of electrolyte for lithium ion battery and lithium ion battery
CN107706455A (en) A kind of high voltage multiplying power electrolyte for taking into account high temperature performance and the lithium ion battery using the electrolyte
CN108808071B (en) Electrolyte for high-nickel ternary positive electrode material system battery and lithium ion battery
CN109921092A (en) A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte
CN109980282A (en) A kind of low temperature resistant non-aqueous electrolyte for lithium ion cell and lithium ion battery
CN110021785A (en) A kind of ternary high-voltage lithium-ion battery electrolyte and ternary high-voltage lithium ion batteries
CN107195966B (en) A kind of high voltage tertiary cathode material system lithium-ion battery electrolytes that high/low temperature performance is taken into account
CN109473713A (en) A kind of high-voltage electrolyte for taking into account high temperature performance and the lithium ion battery using the electrolyte
CN109818064A (en) A kind of high temperature high voltage nonaqueous electrolytic solution and the lithium ion battery containing the nonaqueous electrolytic solution
CN109193029A (en) A kind of nickelic ternary non-aqueous electrolyte for lithium ion cell and the nickelic ternary lithium ion battery containing the electrolyte
CN109346772A (en) A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery
CN104466247B (en) A kind of lithium ion battery of nonaqueous electrolytic solution and the application electrolyte
CN108321434A (en) A kind of high-voltage lithium-ion battery electrolyte
CN109417201A (en) Battery electrolyte additive, lithium-ion battery electrolytes, lithium ion battery
CN109065951A (en) A kind of lithium-ion battery electrolytes and lithium ion battery
CN109888386A (en) A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte
CN107017432A (en) Nonaqueous electrolytic solution and lithium ion battery
CN107863556A (en) The lithium ion battery and its electrolyte that a kind of high-nickel material is positive pole, silicon carbon material is negative pole
CN105977525A (en) Lithium ion battery employing non-aqueous electrolyte
CN109687021A (en) A kind of high temp resistance lithium ion cell nonaqueous electrolytic solution
CN109860709A (en) A kind of electrolyte improving lithium ion battery cryogenic property and the lithium ion battery comprising the electrolyte
CN105261791A (en) Ultra-temperature high-voltage lithium-ion battery electrolyte and lithium-ion battery using electrolyte

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190802

WD01 Invention patent application deemed withdrawn after publication