CN109713367A - A kind of siliceous lithium ion battery with high energy density - Google Patents
A kind of siliceous lithium ion battery with high energy density Download PDFInfo
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Abstract
The present invention relates to a kind of siliceous lithium ion battery with high energy density, including anode, contain silicium cathode, fluorine-containing electrolyte, diaphragm, tab and encapsulating material；Described contains silicium cathode using silica-base material as all or part of electroactive substance；Non-aqueous organic solvent, the SEI film for additive, hydrofluoroether that the electrolyte contains lithium salts, can dissolve lithium salts；Lithium salts is higher than 2mol/L in the solubility of the non-aqueous organic solvent of the dissolvable lithium salts；Solubility of the lithium salts in the hydrofluoroether is lower than 0.3mol/L；The non-aqueous organic solvent of the dissolvable lithium salts dissolves each other with hydrofluoroether；The non-aqueous organic solvent of the dissolvable lithium salts and the SEI film for additive of liquid dissolve each other, and can dissolve solid SEI film for additive.The siliceous lithium ion battery has energy density high, has extended cycle life, and multiplying power property is good, and security performance is high, is not easy the advantages such as to expand, deform.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of siliceous lithium ion battery with high energy density.
Background technique
Due to the fast development of various portable electronic devices, New-energy electric vehicle and energy-storage system in recent years and extensively
General application for energy density height, has extended cycle life, increasingly urgent using the demand of lithium ion battery safe, that multiplying power property is good
It cuts.
The negative electrode material of current commercialized lithium ion battery is mainly graphite, but due to the low (372mAh/ of theoretical capacity
G), the raising of lithium ion battery energy density is limited.The Gao Rong that there are silicon based anode material other negative electrode materials can not be equal to
Amount advantage becomes research and development focus in recent years, and gradually from laboratory, business application is moved towards in research and development.Silicon based anode material is main
There are three types of, first is that elemental silicon or its composite material formed with carbon；Second is that silicon oxide compound or its with carbon material composite material；
Third is that the alloy material that silicon is formed with other metallic elements.Three of the above silicon based anode material all has the appearance for being several times as much as graphite
Amount, therefore application of the silicon based anode material in lithium ion battery makes it possible the further increasing of energy density.On however,
Silicon based anode material is stated in lithium ion battery charge and discharge cycles, lasting embedding de- lithium process will cause silica-base material particle volume
Greatly expansion and contraction.This volume expansion and contraction change repeatedly, will cause the rupture of particle.It is generated after breakage of particles
Fresh silicon materials surface can generate new unstable SEI film with traditional electrolyte.The generation repeatedly of SEI film and thicken from
And limited transportable lithium ion in electrolyte and battery system is persistently consumed, reduce the cycle performance of battery.In addition, containing
The internal resistance that will also result in pole piece and battery for the SEI that silicium cathode continuous surface is formed and thickened during silicon lithium ion circulating battery
It increases, expansion rate rises, so as to cause battery super thick, deformation, the rupture of even battery case.
It is currently applied to the electrolyte of commercialization graphite-based lithium ion battery generally with lithium hexafluoro phosphate (LiPF6) it is used as lithium
Salt, with high viscosity, the cyclic carbonate such as ethylene carbonate (EC) of high dielectric constant, propene carbonate (PC) and low viscosity, low
Dielectric constant linear carbonate such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) are constituted
Mixture is solvent, and the concentration of lithium salts is generally 1~1.5mol/L.Although such electrolyte obtains in graphite-based lithium ion battery
Obtained extensive use, but the poor compatibility of itself and silicon-based anode in siliceous lithium ion battery, it can be in silica-base material continuous surface
Thicker SEI film is formed, causes the efficiency for charge-discharge of lithium ion battery lower, internal resistance steeply rises, and recycles quickly diving, easily swollen
The problems such as bulging deformation.Also, have under such tradition low concentration electrolyte conditions thermal stability it is poor, to moisture-sensitive, high voltage
The problems such as easily decomposing, limits the use temperature range and voltage power supply window of electrolyte, and to electrolyte material therefor
Ambient humidity is more sensitive during water content and electrolyte preparation and battery liquid-filling.
The above problem seriously limits the commercial applications of siliceous lithium ion battery.In view of the above-mentioned problems, scientific research personnel into
The improvement of following aspect is gone.
Authorization Notice No. be CN102005606B Chinese patent literature disclose it is a kind of using fluorinated ethylene carbonate with
And siliceous negative electrode lithium ion secondary cell of the 1,3- propane sultone as electrolysis additive.Authorization Notice No. is
The Chinese patent literature of CN103594730B disclose it is a kind of for silicium cathode lithium battery with the organosilicon isocyanide containing polyether chain
Acid compound is the electrolyte of additive, and the additive can effectively improve the charge-discharge performance of silicium cathode lithium battery, is reduced
The generation of side reaction inhibits battery flatulence, improves cycle life.Authorization Notice No. is the Chinese patent literature of CN103413969B
Disclose it is a kind of using silica-base material as the electrolyte for lithium ion battery of negative electrode material and lithium ion battery, the electrolyte include one
Kind film for additive three (pentafluorophenyl group) borine, which, which helps to be formed on negative electrode material surface, stablizes complete SEI film,
Weaken powder phenomenon-tion caused by the bulk effect of silicon of the silica-base material as negative electrode material when.Authorization Notice No. is
The Chinese patent literature of CN102479973B discloses a kind of silicon cathode lithium ion battery, including electrolysis additive coke diene acid
Propyl diester.The additive will form stable SEI film, alleviates, inhibits reacting between Li-Si alloy and organic solvent.More than
Method is to add on the basis of conventional electrolysis liquid (the organic carbonate weak solution (~1.0M) of lithium hexafluoro phosphate (LiPF6))
Functional additive.For these additives to the performance boosts limited extent such as circulation of siliceous lithium ion battery, high-temperature behavior is poor,
Electrolyte is still inflammable.
Authorization Notice No. is that the Chinese patent literature of CN105845978B discloses a kind of high-energy using silicon-based anode
Density lithium ion battery, the lithium ion battery use polyelectrolyte, the polyelectrolyte include non-aqueous organic solvent,
Lithium salts, the polymer of additive and dispersion in the electrolytic solution, the polymer includes Carboxylic Acid Fibre element and Fluorine containing olefine polymer
Mixture, the additive includes vinyl trialkyl oxysilane.Battery can be made using polyelectrolyte of the invention
In liquid electrolyte be transformed into the gel state for having both excellent mechanical stability and ion transmission performance after high temperature is melted into.One
The caking property of silicon-based anode and diaphragm interface can be improved in aspect, avoids in cyclic process because of silicon-based anode expansion and electrolyte
Interfacial failure caused by consuming；On the other hand, side reaction occurs for the active surface that can slow down organic solvent in silicon-based anode.Make
The cycle performance of silicon-based anode lithium ion battery can be improved with polyelectrolyte of the invention and reduce battery and be circulated throughout
Thickness swelling in journey.Application publication number is that the Chinese patent literature of CN104868165A discloses a kind of gel polymer
Lithium battery preparation method and battery.The electrolyte containing functional additive and polymer monomer is injected in battery core, through overactivation
Polymerize with hot pressing, make electrolyte that polymerization occur while abundant infiltration and form gel state, make anode pole piece, cathode pole piece and every
Film is adhered to each other, and so that battery core is formed entirety, septation is made of polymer coating layer or ceramic coating layer.The invention
The expansion effect of pole piece can also be alleviated while significantly improving battery energy density or be eliminated to gel polymer lithium ion battery
Bring penalty is answered, battery core bulging or deformation are prevented, improves the comprehensive performance and cycle life of battery.However above-mentioned gel
The conductivity at room temperature of polyelectrolyte is lower, causes battery high rate performance poor, and mechanical strength is still not enough to press down
The only electrochemical expansion of silicon materials.
Application publication number is that the Chinese patent literature of CN108232302A discloses one kind suitable for silicon-based anode lithium ion
The high concentration lithium salt electrolyte of battery, including lithium salts and non-aqueous organic solvent, the molar concentration of the lithium salts are 2.15-
4.00mol/L.This high concentration electrolyte electrochemical stability is high, generates the densification by lithium salts anionic derivative in negative terminal surface
SEI film inhibits the continuous formation of silicon based anode material surface SEI film, improves the stability of silicon-based anode and electrolyte interface, from
And capacitance loss of the silicon-based anode in cyclic process is reduced, improve the coulombic efficiency and cycle performance of silicon-based anode.Compared to biography
The electrolyte of the low lithium salt of system, above-mentioned high concentration electrolyte are all formed in conjunction with lithium ion due to most of solvent molecule
Solvation shell structure, therefore electrochemical stability is higher.But the ratio of lithium salts is excessively high in electrolyte, can dramatically increase electricity
The viscosity for solving liquid, reduces the activity of lithium ion, causes being substantially reduced for electrolyte lithium ionic mobility, while being also unfavorable for being electrolysed
As a result good wet between liquid and electrode causes the practical performance capacity of battery lower, multiplying power property is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of siliceous lithium ion battery with high energy density, special electrolyte systems
Energy density height is made it have, is had extended cycle life, multiplying power property is good, and security performance is high, is not easy the advantages such as to expand, deform.
To achieve the above object, the invention provides the following technical scheme:
A kind of siliceous lithium ion battery with high energy density, including anode, contain silicium cathode, fluorine-containing electrolyte, diaphragm, tab
And encapsulating material.
Described contains silicium cathode using silica-base material as all or part of electroactive substance.
Non-aqueous organic solvent, the SEI film for additive, hydrofluoroether that the electrolyte contains lithium salts, can dissolve lithium salts.
Solubility of the lithium salts in the non-aqueous organic solvent of the dissolvable lithium salts is higher than 2mol/L；
Preferably, solubility of the lithium salts in the non-aqueous organic solvent of the dissolvable lithium salts is higher than 3mol/L.
Solubility of the lithium salts in the hydrofluoroether is lower than 0.3mol/L；
Preferably, solubility of the lithium salts in the hydrofluoroether is lower than 0.1mol/L.
The non-aqueous organic solvent of the dissolvable lithium salts dissolves each other with hydrofluoroether.
The non-aqueous organic solvent of the dissolvable lithium salts and the SEI film for additive of liquid dissolve each other, and can dissolve solid
SEI film for additive.
The fluorine-containing electrolyte, mole of the lithium salts in the non-aqueous organic solvent and additive agent mixture that can dissolve lithium salts
Concentration is 1-5mol/L；
Preferably molar concentration of the lithium salts in the non-aqueous organic solvent and additive agent mixture that can dissolve lithium salts is 1-
2.7mol/L。
The fluorine-containing electrolyte, molar concentration of the lithium salts in entire fluorine-containing electrolyte is 0.7-4mol/L；
Preferably, molar concentration of the lithium salts in entire fluorine-containing electrolyte is 0.7-3mol/L；
It is further preferred that molar concentration of the lithium salts in entire fluorine-containing electrolyte is 0.7-1.4mol/L.
The mass fraction of the lithium salts is 9-68%, and the mass fraction that can dissolve the non-aqueous organic solvent of lithium salts is 16-
The mass fraction of 80%, SEI film for additive is 1-25%, and the mass fraction of hydrofluoroether is 10-70%；
Preferably, the mass fraction of the lithium salts is 14-48%, can dissolve the quality point of the non-aqueous organic solvent of lithium salts
Number is 17-50%, and the mass fraction of SEI film for additive is 3-20%, and the mass fraction of hydrofluoroether is 20-60%.
The hydrofluoroether is selected from least one of shown in following general structure (1):
Wherein: R1 is selected from the fluoro-alkyl of C1~C10；
Preferably, R1 is selected from the fluoro-alkyl of C1~C6；
It is further preferred that R1 is selected from the linear fluoroalkyl of C1~C3；
Wherein: R2 is selected from the alkyl of C1~C10 or the fluoro-alkyl of C1~C10,
Preferably, R2 is selected from the alkyl of C1~C6 or the fluoro-alkyl of C1~C6,
It is further preferred that R2 is selected from the alkyl of C1~C3 or the fluoro-alkyl of C1~C3.
The lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB),
Trifluoromethyl sulfonic acid lithium (LiSO3CF3), three (trimethyl fluoride sulfonyl) lithium methide (LiC (CF3SO2)3), bis trifluoromethyl sulphonyl it is sub-
The group of one or more of amine lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI), difluorine oxalic acid boracic acid lithium (LiODFB)
It closes；
Preferably, the lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), double oxalic acid boric acid
Lithium (LiBOB), bis trifluoromethyl sulfimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI), difluorine oxalic acid boracic acid lithium
One or more of (LiODFB) combination.
The non-aqueous organic solvent of the dissolvable lithium salts is from ethylene carbonate (EC), propene carbonate (PC), carbonic acid fourth
Enester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl
Ethyl carbonate ester (EMC), gamma-butyrolacton (GBL), methyl formate (MF), methyl acetate (MA), ethyl propionate (EP), propionic acid third
The combination of one or more of ester (PP), acetonitrile (AN)；
Preferably, the non-aqueous organic solvent of the dissolvable lithium salts is from ethylene carbonate (EC), propene carbonate
(PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethyl propionate (EP), propionic acid third
The combination of one or more of ester (PP).
The SEI film for additive is selected from vinylene carbonate (VC), vinylethylene carbonate (VEC), fluoro carbonic acid second
Enester (FEC), difluorinated ethylene carbonate (DFEC), propylene sulfite (PS), ethylene sulfite (ES), sulfurous acid diformazan
Ester (DMS), sulfurous acid diethyl ester (DES), three (2,2,2- trifluoroethyl) phosphite esters (TTFP), 1,3- propene sultone
(PTS), dimethyl sulfoxide (DMSO), methylchloroformate, 1,4- butane sultones (BS), ethylmethane sulfonate, methane sulfonic acid fourth
Ester, bromo butyrolactone, fluoroacetic base ethane, 1,2- trifluoroacetic acid base ethane (BTE), methyl phenyl ethers anisole, N, N- dimethyl trifluoro second
The combination of one or more of amide (DMTFA), chloroethylene carbonate ester.
Compared with prior art, the present invention specifically having the following advantages:
1. siliceous lithium ion battery of the present invention has used the electrolyte specially researched and developed for silicon based anode material.Institute
Molar concentration of the lithium salts in the mixture of the non-aqueous organic solvent and SEI film for additive that can dissolve lithium salts in the electrolyte stated
It is higher.The hydrofluoroether dissolved each other with non-aqueous organic solvent is added simultaneously, a part of non-aqueous organic solvent of dissolution lithium salts can be seized, made
It is further increased at the molar concentration of lithium salts part, in the regional area, almost all of solvent molecule and anion are involved in
The solvation of lithium ion reduces the free solvent molecule even completely eliminated in lithium salts local electrolyte, lithium ion and solvent point
The complexing power enhancing of son, the energy barrier for restoring solvent are promoted, and the reactivity of electrolyte is reduced significantly, helps to inhibit
Traditional electrolyte is oxidized at higher voltages, can also have been prevented from being reduced at the lower voltage, stablized and wider
Electrochemical window.Silicium cathode SEI film for additive is easier to preferentially restore in negative terminal surface in such high local concentrations electrolyte,
It forms one layer of performance and restores the SEI film to be formed better than existing electrolyte, the further decomposition of electrolyte can be inhibited, and be circulated throughout
Relatively thin thickness and preferable flexibility are remained in journey, therefore, as the cycle progresses, it is aobvious not to occur interface impedance
The case where writing increase, the reduction of lithium ion mobility rate, the circulating battery later period is also able to maintain higher coulombic efficiency and specific capacity.It is wider
Electrochemical window, the charge cutoff voltage of siliceous lithium ion battery can be promoted, without will cause part lithium salts to Al foil
Corrosion, will not cause decomposition of the high-voltage anode to electrolyte.Higher voltage positive electrode uses meeting so that containing silicium cathode
Lithium ion battery energy density obtains raising by a larger margin.Wider electrochemical window but also siliceous lithium ion battery to system
Moisture control during making no longer needs excessive harshness, reduces production environment and controls cost.It is flammable in high concentration electrolyte
Solvent molecule is less, and hydrofluoroether has flame retardant effect, so that the flammable of electrolyte whole reduces.Hydrofluoroether is by high concentration electric
After solving liquid dilution, although local lithium salt has obtained further concentration, electrolyte whole has low viscosity, high-lithium ion
The advantage of the tradition low concentration lithium salt electrolyte such as conductivity and good wellability.
For synthesis, siliceous lithium ion battery of the present invention has high energy density, circulation conservation rate height, multiplying power special
The advantages such as property is good, be not easy to produce gas, be not easy to expand, be unlikely to deform, security feature is good.
Detailed description of the invention
Fig. 1: the surface SEI film electron scanning micrograph of state cathode is detached within battery 50 weeks in embodiment 1 after circulation.
Fig. 2: the surface SEI film electron scanning micrograph of lithium state cathode is taken off within battery 50 weeks in comparative example 1 after circulation.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Hydrofluoroether used in following embodiment and comparative example is as follows:
1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ethers (TTE), 1,1,1,3,3,3- hexafluoro isopropyl methyl ether
(HFME), bis- (2,2,2- trifluoroethyl) ethers (BTFE), ten fluoro- 3- methoxyl group -2- trifluoromethyl pentanes (TMMP).
The preparation of pure silicon negative electrode lithium ion battery mainly has following steps:
The preparation of positive plate: blended anode active material, conductive agent, binder mass percent be 97.5:1:1.5,
Middle positive electrode active material LiCoO2, specific preparation process is as follows: weighing LiCoO in proportion2Positive electrode, conductive black and poly- inclined
Difluoroethylene (PVDF) adhesive powder carries out premixing 30min using double planetary mixing machine, N- is then added in batch can
Methyl pyrrolidone (NMP) is used as solvent, after high-speed stirred 60min, obtain thick anode sizing agent, be uniformly coated on aluminium foil
On, after drying, rolling, pole piece is punched into the small pieces having a size of 52*75mm.
The preparation of negative electrode tab: negative electrode active material, conductive agent, thickener, binder mass percent be 84.5:0.5:5:
10, specific preparation process is as follows: wherein negative electrode active material pure silicon granules material, specific preparation process are as follows: weighing in proportion
Pure silicon negative electrode material, carbon nanotube conducting agent, sodium carboxymethylcellulose (CMC) in batch can, using double planetary mixing machine into
Row premixing 30min, is then added bonding agent (butadiene-styrene rubber (SBR) aqueous emulsion that concentration is 50%, 10% polypropylene sour water
Each half of solution), and it is solvent that appropriate amount of deionized water, which is added, thick negative electrode slurry is made in mechanical mixture, and is uniformly coated with
On copper foil, after drying rolls, pole piece is punched into the small pieces having a size of 53.5*76.5mm.
The assembling of siliceous lithium ion battery: the anode small pieces according to made from previous process, cathode small pieces and diaphragm according to
" Z " font technique stacks poling group, the positive and negative electrode foil in the group of pole is then carried out pre- point respectively on ultrasonic spot welder
Weldering after removing extra foil length, welds aluminium pole ears in positive aluminium strip endpoint respectively, cathode copper strips endpoint welds nickel tab, and in pole
Ear weld sticks protection gummed paper, is then charged into aluminium plastic bag, and pole group, 40 DEG C of agings are made by techniques such as top side seal sealings
Terminate for 24 hours, inject electrolyte and encapsulate, after 40 DEG C of aging 48h, cramping chemical conversion is carried out to battery, then carries out degasification, by battery
It is placed in ageing oven, after 48~72h of aging, carries out partial volume (4.4V-2.75V), then measure size and weight and other are every
Performance test.
Embodiment 1
21.6g EMC, 11.0g FEC are taken, after mixing wherein by 19.4g LiFSI dissolution, 48.0g is then added
TTE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test are carried out
Technique.
A battery is taken, after circulation terminates at 50 weeks, 2.75V cut-off is discharged to, it is clear with DMC that cathode pole piece is taken out after dismantling
Vacuum drying after washing three times, in the SEI film of electric microscopic observation pole piece, as shown in Figure 1, negative terminal surface can be observed from figure
The SEI film of formation is thin, and very fine and close.
Embodiment 2
17.4g EMC, 8.9g FEC are taken, after mixing wherein by 15.6g LiFSI dissolution, 58.1g is then added
TTE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test are carried out
Technique.
Embodiment 3
28.4g EMC, 14.5g FEC are taken, after mixing wherein by 25.5g LiFSI dissolution, 31.6g is then added
TTE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test are carried out
Technique.
Embodiment 4
16.6g EMC, 11.0g FEC are taken, after mixing wherein by 24.4g LiFSI dissolution, 48.0g is then added
TTE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test are carried out
Technique.
Embodiment 5
17.5g EMC, 8.9g FEC are taken, after mixing wherein by 15.6g LiFSI dissolution, 58.0g is then added
HFME is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and survey are carried out
Trial work skill.
Embodiment 6
17.5g EMC, 8.9g FEC are taken, after mixing wherein by LiFSI 15.6g dissolution, 58.0g is then added
BTFE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and survey are carried out
Trial work skill.
Embodiment 7
The battery prepared in Example 6, when test, improve charging voltage to 4.43V.Battery in the comparative example exists
Discovery is disassembled after loop test, corrosion phenomenon does not occur in positive pole aluminium foil.
Comparative example 1
Take 16.0g EC, 54.0g EMC, 15.0g FEC, after mixing by LiPF615.0g dissolution is wherein.By gained
After electrolyte injects above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test technology are carried out.
A battery is taken, after circulation terminates at 50 weeks, 2.75V cut-off is discharged to, it is clear with DMC that cathode pole piece is taken out after dismantling
It is dried in vacuo after washing three times, in the SEI film that electric microscopic observation pole piece is formed, as shown in Fig. 2, can be observed from figure in cathode
The SEI film that surface is formed is very thick and loose porous.
Comparative example 2
Take the battery prepared in comparative example 1, when test improves charging voltage to 4.43V.Battery in the comparative example exists
Discovery is disassembled after loop test, more serious corrosion phenomenon occurs in positive pole aluminium foil.
Comparative example 3
41.5g EMC, 21.2g FEC are taken, after mixing wherein by LiFSI 37.3g dissolution.Gained electrolyte is infused
After entering above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test technology are carried out.
Battery in the comparative example is disassembled after loop test in full power state, finds electrolyte in pole piece and diaphragm
On wellability it is poor, part negative regions have analysis lithium phenomenon.
Comparative example 4
26.2g EMC is taken, LiFSI 15.6g is then added, is added after completely dissolution to lithium salts, 58.2g is then added
TTE is stirred for uniformly.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, further battery preparation and test are carried out
Technique.
Comparative example 5
15.6g EMC, 4.0g FEC are taken, after mixing wherein by LiFSI 32.4g dissolution, 48.0g is then added
TTE is stirred for uniformly, and resulting electrolyte becomes cloudy, and illustrates there is lithium salts precipitation.Gained electrolyte is injected into above-mentioned pure silicon cathode
After lithium ion battery, further battery preparation and test technology are carried out.
Comparative example 6
8.8g EMC, 4.5g FEC are taken, after mixing wherein by LiFSI 7.9g dissolution, 78.8g TTE is then added
It is stirred for uniformly, resulting electrolyte slightly has muddiness.After gained electrolyte is injected above-mentioned pure silicon negative electrode lithium ion battery, carry out
Further battery preparation and test technology.
Above-described embodiment and the electrolyte prescription of comparative example, concentration and test result are summarised in table 1:
Table 1
The preparation for aoxidizing sub- silicon-graphite composite negative pole lithium ion battery mainly has following steps:
The preparation of positive plate: blended anode active material, conductive agent, binder mass percent be 97.1:1.2:1.7,
Wherein positive electrode active material is LiNi0.8Mn0.1Co0.1O2(NMC811), specific preparation process is as follows: weighing NMC811 in proportion just
Pole material, conductive black and polyvinylidene fluoride (PVDF) adhesive powder in batch can, using double planetary mixing machine into
Then row premixing 60min is added N-Methyl pyrrolidone (NMP) and is used as solvent, after high-speed stirred 90min, obtain thick
Anode sizing agent is uniformly coated on aluminium foil, and after drying, rolling, pole piece is punched into the small pieces having a size of 52*75mm.
The preparation of negative electrode tab: the carbon-coated quality for aoxidizing sub- silicon materials, artificial graphite, conductive agent, thickener, binder
Percentage is 12:81.2:0.3:2:4.5, and specific preparation process is as follows: weighing the sub- silicon materials of carbon-coated oxidation, people in proportion
Graphite, single-walled carbon nanotube conductive agent are made, sodium carboxymethylcellulose (CMC) is carried out in batch can using double planetary mixing machine
It is pre-mixed 30min, bonding agent is then added, and (butadiene-styrene rubber (SBR) aqueous emulsion that concentration is 50%, 10% polyacrylic acid are water-soluble
Each half of liquid), and it is solvent that appropriate amount of deionized water, which is added, thick negative electrode slurry, and uniform copper coated is made in mechanical mixture
On foil, after drying rolls, pole piece is punched into the small pieces having a size of 53.5*76.5mm.
The assembling of siliceous lithium ion battery: the anode small pieces according to made from previous process, cathode small pieces and diaphragm according to
" Z " font technique stacks poling group, the positive and negative electrode foil in the group of pole is then carried out pre- point respectively on ultrasonic spot welder
Weldering after removing extra foil length, welds aluminium pole ears in positive aluminium strip endpoint respectively, cathode copper strips endpoint welds nickel tab, and in pole
Ear weld sticks protection gummed paper, is then charged into aluminium plastic bag, and pole group, 40 DEG C of agings are made by techniques such as top side seal sealings
Terminate for 24 hours, injection electrolyte simultaneously encapsulate, after 40 DEG C of aging 48h, cramping chemical conversion is carried out to battery, then carries out degasification, then into
Row degasification, battery is placed in ageing oven, after 48~72h of aging, carry out partial volume (4.25V-2.75V), then measure size and
Weight and the test of other properties.
Embodiment 8
10.20g PC, 4.10g EP, 11.30g PP, 2.70g FEC, 0.68g VEC, 0.34g PS are successively weighed, is mixed
After closing uniformly, it is separately added into 2.73g LiBF4, 8.19g LiFSI, 12.29g LiPF6, 12.29g LiODFB, 1.23g
LiTFSI, 1.23g LiBOB dissolve wherein, and 32.41g BTTE is then added and is stirred for uniformly.Gained electrolyte is injected and is aoxidized
After sub- silicon-graphite composite negative pole lithium ion battery, further battery preparation and test technology are carried out.
Embodiment 9
13.30g PC, 5.30g EP, 14.60g PP, 3.5g FEC, 0.87g VEC, 0.44g PS are successively weighed, is mixed
After uniformly, it is separately added into 1.00g LiBF4, 3.00g LiFSI, 4.50g LiPF6, 4.50g LiODFB, 0.45g LiTFSI,
0.45g LiBOB dissolves wherein, and 48.00g BTTE is then added and is stirred for uniformly.Gained electrolyte is injected and aoxidizes sub- silicon-stone
After black composite negative pole lithium ion battery, further battery preparation and test technology are carried out.
Embodiment 10
13.30g PC, 5.30g EP, 14.60g PP, 3.5g FEC, 0.87g VEC, 0.44g PS are successively weighed, is mixed
After uniformly, it is separately added into 1.00g LiBF4, 3.00g LiFSI, 4.50g LiPF6, 4.50g LiODFB, 0.45g LiTFSI,
0.45g LiBOB dissolves wherein, and 48.00g HFME is then added and is stirred for uniformly.Gained electrolyte is injected and aoxidizes sub- silicon-stone
After black composite negative pole lithium ion battery, further battery preparation and test technology are carried out.
Embodiment 11
13.30g PC, 5.30g EP, 14.60g PP, 3.5g FEC, 0.87g VEC, 0.44g PS are successively weighed, is mixed
After uniformly, it is separately added into 1.00g LiBF4, 3.00g LiFSI, 4.50g LiPF6, 4.50g LiODFB, 0.45g LiTFSI,
0.45g LiBOB dissolves wherein, and 48.00g TMMP is then added and is stirred for uniformly.Gained electrolyte is injected and aoxidizes sub- silicon-stone
After black composite negative pole lithium ion battery, further battery preparation and test technology are carried out.
Embodiment 12
13.30g PC, 5.30g EP, 14.60g PP, 3.5g FEC, 0.87g VEC, 0.44g PS are successively weighed, is mixed
After uniformly, it is separately added into 1.00g LiBF4, 3.00g LiFSI, 4.50g LiPF6, 4.50g LiODFB, 0.45g LiTFSI,
0.45g LiBOB dissolves wherein, and 24.00g TTE is then added, and 24.00g BTFE is stirred for uniformly.Gained electrolyte is injected
After aoxidizing sub- silicon-graphite composite negative pole lithium ion battery, further battery preparation and test technology are carried out.
Comparative example 7
30.00g PC, 12.00g EP, 33.00g PP, 8.00g FEC, 2.00g VEC, 1.00g PS are successively weighed, is mixed
After closing uniformly, it is separately added into 1.00g LiBF4, 3.00g LiFSI, 4.50g LiPF6, 4.50g LiODFB, 0.45g
LiTFSI, 0.45g LiBOB dissolve wherein, and stir evenly.Gained electrolyte is injected and aoxidizes sub- silicon-graphite composite negative pole lithium
After ion battery, further battery preparation and test technology are carried out.
Battery in the comparative example disassembles discovery after loop test, and it is existing that slighter corrosion occurs in positive pole aluminium foil
As.
Comparative example 8
15.20g PC, 6.06g EP, 16.70g PP, 4.00g FEC, 1.01g VEC, 0.51g PS are successively weighed, is mixed
After closing uniformly, it is separately added into 4.04g LiBF4, 12.12g LiFSI, 18.18g LiPF6, 18.18g LiODFB, 1.82g
LiTFSI, 1.82g LiBOB dissolve wherein, and stir evenly.Gained electrolyte is injected and aoxidizes sub- silicon-graphite composite negative pole lithium
After ion battery, further battery preparation and test technology are carried out.
Battery in the comparative example is disassembled after loop test in full power state, finds electrolyte in pole piece and diaphragm
On wellability it is bad, the embedding lithium of negative terminal surface is uneven, part negative regions be not golden yellow, illustrate the region due to there is no electricity
It solves the infiltration of liquid and fails abundant embedding lithium, and there is analysis lithium in part negative regions.
Comparative example 9
14.00g PC is successively weighed, 5.58g EP, 15.40g PP is separately added into 1.05g LiBF after mixing4,
3.15g LiFSI, 4.73g LiPF6, 4.73g LiODFB, 0.47g LiTFSI, 0.47g LiBOB dissolve wherein, subsequent to add
Enter 50.00g BTFE to be stirred for uniformly.Gained electrolyte is injected after aoxidizing sub- silicon-graphite composite negative pole lithium ion battery, into
The preparation of row further battery and test technology.
Above-described embodiment and the electrolyte prescription of comparative example, concentration and test result are summarised in table 2:
Table 2
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (7)
1. a kind of siliceous lithium ion battery with high energy density, it is characterised in that: including anode, containing silicium cathode, fluorine-containing electrolyte,
Diaphragm, tab and encapsulating material；
Described contains silicium cathode using silica-base material as all or part of electroactive substance；
Non-aqueous organic solvent, the SEI film for additive, hydrofluoroether that the electrolyte contains lithium salts, can dissolve lithium salts；
Solubility of the lithium salts in the non-aqueous organic solvent of the dissolvable lithium salts is higher than 2mol/L；
Solubility of the lithium salts in the hydrofluoroether is lower than 0.3mol/L；
The non-aqueous organic solvent of the dissolvable lithium salts dissolves each other with hydrofluoroether；
The non-aqueous organic solvent of the dissolvable lithium salts and the SEI film for additive of liquid dissolve each other, can dissolve solid SEI at
Film additive.
2. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: lithium salts is in dissolvable lithium
Molar concentration in the non-aqueous organic solvent of salt and the mixture of SEI film for additive is 1-5mol/L；Lithium salts is entire fluorine-containing
Molar concentration in electrolyte is 0.7-4mol/L.
3. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: in the electrolyte
In, the mass fraction of the lithium salts is 9-68%, and the mass fraction that can dissolve the non-aqueous organic solvent of lithium salts is 16-80%, SEI
The mass fraction of film for additive is 1-25%, and the mass fraction of hydrofluoroether is 10-70%.
4. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: the hydrofluoroether choosing
From at least one of shown in following general structure (1):
Wherein: R1 is selected from the fluoro-alkyl of C1~C10；
R2 is selected from the alkyl of C1~C10 or the fluoro-alkyl of C1~C10.
5. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: the lithium salts is selected from
Lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium
(LiSO3CF3), three (trimethyl fluoride sulfonyl) lithium methide (LiC (CF3SO2)3), it is bis trifluoromethyl sulfimide lithium (LiTFSI), double
The combination of one or more of fluorine sulfimide lithium (LiFSI), difluorine oxalic acid boracic acid lithium (LiODFB).
6. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: the dissolvable lithium
The non-aqueous organic solvent of salt is selected from ethylene carbonate (EC), propene carbonate (PC), butylene (BC), dimethyl carbonate
(DMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), γ-
Butyrolactone (GBL), methyl formate (MF), methyl acetate (MA), ethyl propionate (EP), propyl propionate (PP), in acetonitrile (AN)
One or more kinds of combinations.
7. siliceous lithium ion battery with high energy density according to claim 1, it is characterised in that: the SEI film forming adds
Agent is added to be selected from vinylene carbonate (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), two fluoro carbonic acid second
Enester (DFEC), propylene sulfite (PS), ethylene sulfite (ES), dimethyl sulfite (DMS), sulfurous acid diethyl ester
(DES), three (2,2,2- trifluoroethyl) phosphite esters (TTFP), 1,3- propene sultone (PTS), dimethyl sulfoxide (DMSO),
Methylchloroformate, 1,4- butane sultones (BS), ethylmethane sulfonate, butyl methyl sulfonate, bromo butyrolactone, fluoroacetic
Base ethane, 1,2- trifluoroacetic acid base ethane (BTE), methyl phenyl ethers anisole, N, N- dimethyl trifluoroacetamide (DMTFA), chloroethylene carbonate
The combination of one or more of ester.
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