CN105514487A - Method for matching organic silicon electrolyte with silicon-based electrode material for use - Google Patents
Method for matching organic silicon electrolyte with silicon-based electrode material for use Download PDFInfo
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Abstract
The present invention relates to a kind of methods that organosilicon electrolyte and silicon based electrode material mating use, silicon based anode material is silicon powder, aoxidizes sub- silicon or silico-carbo combination electrode material, organosilicon electrolyte includes lithium salts, electrolysis additive and organo-silicon compound, and the organo-silicon compound are as shown in the following general formula:
Wherein, R ', R ", R " ' it is selected from identical or different C1-C10 alkyl, alkoxy or halogen substituent group (- F); M is that C1-C20 alkyl or structure are the-segment of (CH2) nO [(CH2) mO] x (CH2) y structure, and n, m are the integer of 0-10, and x, y are the integer of 0-10; FG is cyano, carbonic ester, polyether chain or tertiary amine groups functional group. The present invention utilizes " similar compatibility " property of organosilicon electrolyte and silicon based electrode material, and the battery produced has Low ESR, excellent cyclical stability and high rate performance and safety.
Description
Technical field
The invention belongs to electrochemical energy storage technical field, be specifically related to a kind of method of organosilicon electrolyte and the use of silicon based electrode material fit.
Background technology
Along with the deterioration increasingly of exhaustion and the terrestrial climate day by day of fossil energy, development of new clean energy resource and reinforcement energy-saving and emission-reduction become the prior development direction of countries in the world.In recent years along with hybrid vehicle and pure electric automobile and new forms of energy (solar energy, wind-powered electricity generation) grid-connected power station project construction paces are accelerated, high-performance power (energy storage) battery becomes one of core technology greatly developed, and current lithium ion battery becomes the most competitive power solution because of advantages such as its high voltage, Large Copacity, cycle performance are good, low stain.The negative material of research and development excellent performance is one of key improving performance of lithium ion battery.Material with carbon element is the negative material of being used widely in business lithium battery, but capacitance density is low, irreversible loss is large, high temperature time fail safe low, overcharge time the shortcoming such as easy short circuit limit the development of carbon negative pole material.Therefore, the Novel cathode material for lithium ion battery that development capacity density is high, cycle performance is excellent and security performance is excellent is extremely urgent.
In numerous Novel cathode material for lithium ion battery, silicon based anode material has the high power capacity advantage (Li that other negative material cannot be equal to
22si
5, theoretical lithium storage content 4200mAh/g), be the negative material that the generally acknowledged next generation has Commercial Prospect.Silicon based anode material is 11 times of current business carbon negative pole material theoretical capacity, and lithium embeds the common embedding voltage of current potential (lower than 0.5V) lower than common solvent molecule of silicon, higher than the deposition potential of lithium.Therefore, silicon based anode material can solve the problem that solvent molecule embeds and Li dendrite is separated out.But silica-base material poorly conductive, there is serious bulk effect in it in doff lithium process, and volume change is about 400%, and electrode material efflorescence and electrode material can be caused to be separated with collector simultaneously.The above-mentioned defect of silica-base material seriously limits its business-like application.For overcoming the bulk effect of silicon, people's silica-base material adopting preparation nanostructure more, silicon thin film material, porous silica material and silicon based composite material improve the cycle performance of silicon based electrode material, but the silicon in this type of composite material can be exposed in electrolyte, due to the bulk effect in charge and discharge process, silicon based electrode material constantly forms unsalted surface, therefore continue to consume electrolyte to generate SEI film, reduce the cycle performance of electrode material.In recent years, the electrolyte matched about silicon based electrode material also has to be reported in succession, as AurbachD., when MullinsCB finds the solvent of fluorinated ethylene carbonate as electrolyte respectively, significantly can improve the cycle performance (J.Langmuir of nano silicon-based electrode lithium ion battery, 2012,28,965-976; 2014,30,7414-7424; Chem.Commun.2012,48,7268-7270).Therefore, by researching and developing with the electrolyte system of silicon based electrode match materials to improve the chemical property of silicon-based anode lithium ion battery, and then develop the new type lithium ion battery of height ratio capacity, high charge-discharge efficiencies, long circulation life, there is certain theory value and practice significance, the development of the technology upgrading and New Energy Industry, electric automobile and hybrid electric vehicle industry that promote lithium ion battery industry is had great importance undoubtedly.
Organo-silicon compound have the advantages such as excellent thermal stability, high conductivity, nontoxicity, low combustible and high de-agglomeration voltage, compare with current business-like organic carbonate electrolyte and there is better security performance, in electrochemical energy storing device, have huge commercial application prospect.Inventor herein has applied for a series of lithium ion battery organosilicon electrolyte material in recent years, comprise organosilicon cyanogen compound (ZL201010182978.6), organosilicon ionic liquid (CN102372732A), silicone carbonate (ZL201210358351.0, PCTCN2012084205), organic silicon amine compound (ZL201010607369.0 and US9,085,591B2), organic silicon-fluorine polyether compound (CN2012103896591/PCLBN2012084192).In view of the high power capacity negative pole that silicon based electrode material is possibility large-scale commercial of future generation, and the great market of the lithium ion battery of applying silicon base electrode material, use organo-silicon compound to be applied to silicon based electrode as electrolyte and also seem particularly important.
Summary of the invention
The present invention utilizes organosilicon electrolyte material and silicon based electrode material " similar compatibility " character, the compatibility that (as cyano group, carbonate group, polyether chain, halogen group, tertiary amine groups etc.) improve organo-silicon compound and silicon-based anode is modified by different functional groups, a kind of method that organosilicon electrolyte and silicon based electrode material fit use is provided, organo-silicon compound are applied to as electrolyte the technique effect that silicon based electrode has outstanding performance, and have Low ESR, excellent cyclical stability and high rate performance and fail safe.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of method that organosilicon electrolyte and silicon based electrode material fit use, described silicon based electrode material is silica flour, is oxidized sub-silicon or silico-carbo combination electrode material, described organosilicon electrolyte comprises lithium salts, electrolysis additive and organo-silicon compound, and described organo-silicon compound are as shown in following general formula:
Wherein, R ', R ", R " ' be selected from identical or different C1-C10 alkyl, alkoxy or halogen substituting group (-F), wherein alkoxy grp is following structure-(CH
2)
no (CH
2cH
2o)
mcH
3, n, m are the integer of 0-10; M is C1-C20 alkyl or structure is-(CH
2)
no [(CH
2)
mo] x (CH
2) segment of y structure, n, m are the integer of 0-10, and x, y are the integer of 0-10; FG is the functional groups such as cyano group, carbonic ester, polyether chain or tertiary amine groups.
Preferably, the structural formula of described organo-silicon compound is cyano-containing organo-silicon compound:
Wherein, R
1, R
2, R
3be selected from identical or different C1-C10 alkyl, alkoxy or halogen substituting group (-F), wherein alkoxyl is following structure-(CH
2)
no (CH
2cH
2o)
mcH
3, n, m are the integer of 0-10; R
4for C1-C20 alkyl.Cyano-containing organo-silicon compound comprise following structure:
Preferably, the structural formula of described organo-silicon compound is halosilanes functionalized carbon acid esters organo-silicon compound:
Wherein, R
5be selected from following group: [-(CH
2)
m-, m=1 ~ 3] or [-(CH
2)
mo (CH
2)
n-, m, n=1 ~ 3]; R
6, R
7, R
8be selected from following group: [-(CH
2)
mcH
3, m=0 ~ 3], aryl or substituted aryl, or halogenic substituent, and R
6, R
7, R
8has a halogen substiuted group at least.The preferred following structure of halosilanes functionalized carbon acid esters organo-silicon compound:
Preferably, the structural formula of described organo-silicon compound is halosilanes functionalization polyethers organo-silicon compound:
Wherein, R
9, R
10, R
11be selected from identical or different-(CH
2) xCH
3, x=0 ~ 5, or halogenic substituent, described halogen is selected from F or Cl, and R
9, R
10, R
11in have a halogenic substituent at least; R
12be structural formula be-NR
13r
14tertiary amine groups, R
13, R
14be selected from the alkyl of identical or different C1-C5; M is the integer of 1-20, and n is the integer of 0-5.The preferred following structure of halosilanes functionalization polyethers organo-silicon compound:
Preferably, the structural formula of described organo-silicon compound is for containing polyether chain organic silicon amine compounds:
Wherein, R
15, R
16be selected from identical or different C1-C10 alkyl; A is as (CH
2)
no [(CH
2)
mo] x (CH
2) polyether segment of y structure, n, m are the integer of 0-10, and x is the integer of 1-10; R
17, R
18and R
19be selected from alkyl or the alkoxy grp of identical or different C1-C10, or structure is equal to ANR
15r
16, or-O-SiR
20r
21r
22, R
20, R
21and R
22for the alkyl of identical or different C1-C10.Containing the preferred following structure of polyether chain organic silicon amine compounds:
Preferably, described lithium salts is selected from LiClO
4, LiPF
6, LiBF
4, LiTFSI, LiFSI, LiBOB, LiODFB, LiCF
3sO
3, LiAsF
6in one or more; Described electrolysis additive be selected from fluorinated ethylene carbonate, propane sultone, vinylene carbonate, succinonitrile, LiBOB, LiODFB one or more.
Preferably, described organo-silicon compound are present in described organosilicon electrolyte as additive agent electrolyte or cosolvent.The mass content that organo-silicon compound are used for electrolyte solvent is 1-100%, remaining solvent is for conventional carbonate organic solvent is (as ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, Deng), ether organic solvent is (as 1,3-dioxolanes, dimethoxymethane, 1,2-dimethoxy, diethylene glycol dimethyl ether, etc.) in any one or a few.
Preferably, the method is applied to electrochemical energy storing device, and described electrochemical energy storing device comprises the sulfenyl lithium battery, metal ion battery, metal-air cell and the super capacitor that use silicon based electrode material.The battery utilizing organosilicon electrolyte of the present invention and silicon based electrode material fit to make has Low ESR, excellent cyclical stability and high rate performance and fail safe.
Preferably, the method is applied to lithium ion battery.
The invention has the beneficial effects as follows: the present invention utilizes " similar compatibility " character of silicon based anode material and organosilicon electrolyte material, organo-silicon compound are applied to silicon-based anode as electrolyte and show outstanding technique effect, and the battery utilizing it to make has Low ESR, excellent cyclical stability and high rate performance and fail safe.
Accompanying drawing explanation
Accompanying drawing 1:Si/C electrode uses the battery charging and discharging cycle performance test curve adding different content BNS electrolyte;
Accompanying drawing 2: electrolyte 1MLiPF
6/ BNS tests the CV curve of Si negative pole;
Accompanying drawing 3:Si and Si/C electrode use electrolyte LB303, LB303+10%FEC, LB303+10%BNS circulating battery test curve;
Fig. 4: electrolyte LB303 and add the testing impedance of Si/Li half-cell of 10wt.%SN1
Fig. 5: electrolyte LB303 and add the testing impedance of Si/Li half-cell of 1wt.%, 5wt.%SN1
Fig. 6: Si electrode uses electrolyte LB303, LB303+0.1wt.%DMSCN circulating battery test curve
Fig. 7: electrolyte LB303, and the Si/Li half-cell charge-discharge performance test curve adding FEC, MFGC, TFGC
Fig. 8: electrolyte LB303, and the Si/Li half-cell charge-discharge performance test curve adding 5wt%TN2
Fig. 9: electrolyte LB303 and add the testing impedance of Si/Li half-cell of 0.5wt.%, 1wt.%DN1
Figure 10: Si electrode uses electrolyte LB303, LB303+0.5wt.%DN2 circulating battery test curve;
Figure 11: electrolyte LB303, and the Si/Li half-cell charge-discharge performance test curve adding 5wt% and 10wt%DFSM2.
Embodiment
Below in conjunction with instantiation, illustrate the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technical staff and adjustment, still belong to protection scope of the present invention in actual applications.
Except special instruction, the equipment that the present invention uses and reagent are the conventional commercial products of the art.
Nano Si and Si/C composite battery cathode pole piece make
In carried out experiment, using nano Si (30 ~ 50nm) and Si/C material as active material, CMC as binding agent, acetylene black is as conductive agent, be 7:1:2 mixing by mass percentage, ball milling 1h prepares mixed slurry, film, on Copper Foil base flow body, is placed in vacuum drying oven 80 DEG C of dryings 24 hours, prepares Si and Si/C electrode.
Embodiment 1
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); Add in above-mentioned basic electrolyte and account for electrolyte gross mass 5%, the BNS of 10% and 20% prepares mixed electrolytic solution, then with Si or Si/C negative pole for work electrode, be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) respectively with mixed electrolytic solution.The concrete method of testing of battery: room temperature 25 DEG C, silicon-based anode half-cell is carried out constant current charge-discharge test on the new prestige battery charging and discharging test macro of Shenzhen, discharge and recharge cut-ff voltage scope is 0 ~ 1.5V, and charging and discharging currents density is 400mA/g, circulates 100 times.Test result is shown in Fig. 1 and Fig. 2.
Fig. 1 is that Si/C electrode uses the battery charging and discharging cycle performance test curve adding different content BNS electrolyte, add 10%BNS battery as seen from the figure and there is best cycle performance, coulombic efficiency 82% first, first discharge specific capacity 1389mAh/g, after 100 circulations, specific capacity is 1035mAh/g, capability retention 74.5%.Fig. 2 is electrolyte 1MLiPF
6/ BNS tests the CV curve of Si negative pole, visible in figure, and electrolyte is first in circulating reduction process, and having obvious reduction peak in 1.7V and 1.1V position, should be that BNS is decomposed to form SEI film at electrode surface, and in the second circle circulation disappearance.
Comparative example 1
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1).Then with Si or Si/C negative pole for work electrode, being to electrode with lithium sheet, take polyethylene film as barrier film, prepares button half-cell (CR2025) by this basic electrolyte.The concrete method of testing of battery is with embodiment 1, and test result is shown in Fig. 3.
Comparative example 2
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the fluorinated ethylene carbonate (FEC) accounting for electrolyte gross mass 10% prepare mixed electrolytic solution, then with Si or Si/C negative pole for work electrode, be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) with this mixed electrolytic solution.The concrete method of testing of battery is with embodiment 1, and test result is shown in Fig. 3.
Fig. 3 is that Si and Si/C electrode uses electrolyte LB303, LB303+10%FEC, LB303+10%BNS circulating battery test curve, as seen from the figure, use electrolyte LB303, LB303+FEC, LB303+BNS, the first discharge specific capacity of Si electrode battery is respectively 3509,3575,3894mAh/g, coulombic efficiency is respectively 77.1 first, and 86.4,86.2%, after 100 circulations, specific discharge capacity is respectively 136,1305,2047mAh/g, capability retention is respectively 5.0, and 41.7,60.8%.And 502,876,1035mAh/g are respectively for the specific discharge capacity of Si/C electrode battery after 100 circulations, and capability retention is 46.9,78.6,88.1%.So for Si and Si/C electrode, LB303+BNS electrolyte battery is used all to have best cycle performance.
Embodiment 2
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the BNS accounting for electrolyte gross mass 3% prepare mixed electrolytic solution, then (be oxidized sub-silicon to be oxidized sub-silicium cathode for work electrode and derive from Shenzhen Bei Terui company, Si/Carbonblack/Binder=60/30/10), be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) respectively with mixed electrolytic solution.The concrete method of testing of battery: room temperature 25 DEG C, sub-for oxidation silicon half-cell is carried out constant current charge-discharge test on the new prestige battery charging and discharging test macro of Shenzhen, and discharge and recharge cut-ff voltage scope is 0 ~ 1.5V, and charging and discharging currents density is 100mA/g.Test result is in table 1.
Comparative example 3
Adopt the method that embodiment 2 is identical to make battery, add the cycle performance of test battery as a comparison with 3% vinylene carbonate (VC), test result is in table 1, table 1 is oxidation sub-silicon electrode use LB303, the loop-around data of LB303+3%VC, LB303+3%BNS, as shown in table 1.
Table 1
As can be seen from Table 1, be oxidized sub-silion cell after with the addition of 3%BNS, in capacity, efficiency for charge-discharge first, have outstanding effect.
Embodiment 3
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the SN1 accounting for electrolyte gross mass 10% prepare mixed electrolytic solution, then with Si negative pole for work electrode, be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) respectively with mixed electrolytic solution.The concrete method of testing of battery: room temperature 25 DEG C, silicium cathode half-cell is carried out testing impedance on electrochemical workstation, and test result is shown in Fig. 4, after adding SN1, the impedance of battery obviously reduces.
Embodiment 4
With DESCN and DMSCN for additive, configure electrolyte according to the mode of embodiment 1, make battery and test, test result as shown in Figure 5, Figure 6.Fig. 5 is that Si electrode uses electrolyte LB303, and adds battery ac impedance measurement after 3 charge and discharge cycles of DESCN electrolyte.Impedance spectrum is visible, and after adding DESCN, the resistance value of battery obviously reduces: be about 36 Ω containing 1%DESCN battery impedance value; 80 Ω are about containing 5%DESCN battery impedance value.And LB303 battery membranes resistance value is about 200 Ω.Less membrane impedance is conducive to the fast transport of lithium ion.
Fig. 6 is electrolyte LB303, and adds the Si/Li half-cell charge-discharge performance test curve of 0.1%DMSCN.Visible on figure, add 0.1%DMSCN, the charge specific capacity before and after 33 circulations is respectively 3130mAh/g and 1921mAh/g, and the charge specific capacity before and after the circulating battery of LB303 is respectively 2440mAh/g and 1502mAh/g.The a small amount of DMSCN of visible interpolation can significantly improve the capacity of battery, improves battery performance.
Embodiment 5
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the MFGC accounting for electrolyte gross mass 3%, then with Si negative pole for work electrode, being to electrode with lithium sheet, take polyethylene film as barrier film, prepares button half-cell (CR2025) with this electrolyte.The concrete method of testing of battery: room temperature 25 DEG C, silicon-based anode half-cell is carried out constant current charge-discharge test on the new prestige battery charging and discharging test macro of Shenzhen, discharge and recharge cut-ff voltage scope is 0 ~ 1.5V, and charging and discharging currents density is 500mA/g, circulates 100 times.Test result is shown in Fig. 7.
Embodiment 6
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); The TFGC accounting for electrolyte gross mass 3% is added in above-mentioned basic electrolyte.Battery assembling and test are with embodiment 1, and test result is shown in Fig. 7.
Comparative example 4
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1).Battery assembling and test are with embodiment 1, and test result is shown in Fig. 7.
Comparative example 5
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); The FEC accounting for electrolyte gross mass 3% is added in above-mentioned basic electrolyte.Battery assembling and test are with embodiment 1, and test result is shown in Fig. 7.
Fig. 7 is electrolyte LB303, and adds the Si/Li half-cell charge-discharge performance test curve of FEC, MFGC, TFGC, as seen from the figure, electrolyte LB303, and add FEC, MFGC, the battery first discharge specific capacity of TFGC is respectively 2945.7,3039,260.4,2720.9mAh/g, after 100 circulations, specific discharge capacity is respectively 808.9,1149.6,1127.1,1458.6mAh/g, capability retention is respectively 27.5,37.8,38.0,53.6%.Add the cycle performance of TFGC to battery to be significantly improved, show as best cyclical stability.FEC and MFGC specific capacity after 100 circulations is close, but all higher than the LB303 not containing additive.Show that three kinds of additives are all improved cycle performance of battery.
Embodiment 7
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the TN2 accounting for electrolyte gross mass 5% prepare mixed electrolytic solution.Battery assembling and test are with embodiment 1, and test result is shown in Fig. 8.
Comparative example 6
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1).Battery assembling and test are with embodiment 1, and test result is shown in Fig. 8.
Fig. 8 is electrolyte LB303, and adds the Si/Li half-cell charge-discharge performance test curve of 5wt%TN2.As seen from the figure, before adding the battery of TN2,40 circle circulation volumes are significantly improved, and higher than basic electrolyte, but its decay is very fast, and after 40 circles, capacity and basic electrolyte maintain an equal level.
Embodiment 8
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the DN1 accounting for electrolyte gross mass 0.5% prepare mixed electrolytic solution, then with Si negative pole for work electrode, be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) respectively with mixed electrolytic solution.The concrete method of testing of battery: room temperature 25 DEG C, silicium cathode half-cell is carried out testing impedance on electrochemical workstation, and test result is shown in Fig. 9.
Embodiment 9
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); In above-mentioned basic electrolyte, add the DN2 accounting for electrolyte gross mass 0.5% prepare mixed electrolytic solution.Battery assembling is with embodiment 7, and constant current charge-discharge test on the new prestige battery charging and discharging test macro of Shenzhen, discharge and recharge cut-ff voltage scope is 0 ~ 1.5V, and charging and discharging currents density is 500mA/g, and circulate 200 times, test result is shown in Figure 10.
Fig. 9 is respectively electrolyte LB303, and the testing impedance figure before the Si/Li half-cell circulation of interpolation 0.5wt%DN1, and as seen from the figure, after adding DN1, the impedance of battery obviously reduces.Figure 10 is respectively electrolyte LB303, and adds the Si/Li half-cell charge-discharge performance test curve of 0.5wt%DN2.As seen from the figure, and discharge and recharge initial cycles capacity and basic electrolyte maintain an equal level, but cyclical stability is significantly improved, and 60 circle circulation volumes are still far above basic electrolyte.
Embodiment 10
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1); Add in above-mentioned basic electrolyte and account for electrolyte gross mass 5%, the DFSM2 of 10% prepares mixed electrolytic solution, then with Si negative pole for work electrode, be to electrode with lithium sheet, take polyethylene film as barrier film, prepare button half-cell (CR2025) respectively with mixed electrolytic solution.The concrete method of testing of battery: room temperature 25 DEG C, silicon-based anode half-cell is carried out constant current charge-discharge test on the new prestige battery charging and discharging test macro of Shenzhen, discharge and recharge cut-ff voltage scope is 0 ~ 1.5V, and charging and discharging currents density is 500mA/g, circulates 200 times.Test result is shown in Figure 11.
Comparative example 7
Be less than in the argon gas glove box of 10ppm at moisture content and oxygen content, preparation lithium-ion battery electrolytes: by 1MLiPF
6/ (electrolyte LB303 based on the electrolyte of EC:DEC:DMC (v:v:v=1:1:1).Battery assembling and test are with embodiment 1, and test result is shown in Figure 11.
Figure 11 is electrolyte LB303, and adds the Si/Li half-cell charge-discharge performance test curve of 5wt% and 10wt%DFSM2.As seen from the figure, add the cycle performance of DFSM2 to battery to have clear improvement.LB303, the battery first discharge specific capacity of adding 5wt% and 10wt%DFSM2 is respectively 2702.7,2263.8,2883.7mAh/g, and after 100 circulations, capability retention is respectively 32.8,52.6,55% (86 circle).After particularly with the addition of 10%DFSM2, no matter be in discharge capacity or cyclical stability, be all obviously better than basic electrolyte.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and this embodiment is also not used to limit the scope of the claims of the present invention, and the equivalence that all the present invention of disengaging do is implemented or changed, and all should be contained in the scope of patent protection of this case.
Claims (10)
1. the method for an organosilicon electrolyte and the use of silicon based electrode material fit, it is characterized in that, described silicon based anode material is silica flour, is oxidized sub-silicon or silico-carbo combination electrode material, described organosilicon electrolyte comprises lithium salts, electrolysis additive and organo-silicon compound, and described organo-silicon compound are as shown in following general formula:
Wherein, R ', R ", R " ' be selected from identical or different C1-C10 alkyl, alkoxy or halogen substituting group (-F), wherein alkoxy grp is following structure-(CH
2)
no (CH
2cH
2o)
mcH
3, n, m are the integer of 0-10; M is C1-C20 alkyl or structure is-(CH
2)
no [(CH
2)
mo] x (CH
2) segment of y structure, n, m are the integer of 0-10, and x, y are the integer of 0-10; FG is cyano group, carbonic ester, polyether chain or tertiary amine groups functional group.
2. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, the structural formula of described organo-silicon compound is cyano-containing organo-silicon compound:
Wherein, R
1, R
2, R
3be selected from identical or different C1-C10 alkyl, alkoxy or halogen substituting group (-F), wherein alkoxyl is following structure-(CH
2)
no (CH
2cH
2o)
mcH
3, n, m are the integer of 0-10; R
4for C1-C20 alkyl.
3. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, the structural formula of described organo-silicon compound is halosilanes functionalized carbon acid esters organo-silicon compound:
Wherein, R
5be selected from following group: [-(CH
2)
m-, m=1 ~ 3] or [-(CH
2)
mo (CH
2)
n-, m, n=1 ~ 3]; R
6, R
7, R
8be selected from following group: [-(CH
2)
mcH
3, m=0 ~ 3], aryl or substituted aryl, or halogenic substituent (-F), and R
6, R
7, R
8has a halogen substiuted group at least.
4. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, the structural formula of described organo-silicon compound is halosilanes functionalization polyethers organo-silicon compound:
Wherein, R
9, R
10, R
11be selected from identical or different-(CH
2) xCH
3, x=0 ~ 5, or halogenic substituent, described halogen is selected from F or Cl, and R
9, R
10, R
11in have a halogenic substituent at least; R
12for alkoxyl or structural formula are-NR
13r
14tertiary amine groups, R
13, R
14be selected from the alkyl of identical or different C1-C5; M is the integer of 1-20, and n is the integer of 0-5.
5. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, is characterized in that, the structural formula of described organo-silicon compound is for containing polyether chain organic silicon amine compounds:
Wherein, R
15, R
16be selected from identical or different C1-C10 alkyl; A is as (CH
2)
no [(CH
2)
mo] x (CH
2) polyether segment of y structure, n, m are the integer of 0-10, and x is the integer of 1-10; R
17, R
18and R
19be selected from alkyl or the alkoxy grp of identical or different C1-C10, or structure is equal to ANR
15r
16, or-O-SiR
20r
21r
22group, R
20, R
21and R
22for the alkyl of identical or different C1-C10.
6. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, described lithium salts is selected from LiClO
4, LiPF
6, LiBF
4, LiTFSI, LiFSI, LiBOB, LiODFB, LiCF
3sO
3, LiAsF
6in one or more; Described electrolysis additive is selected from fluorinated ethylene carbonate, one or more in propane sultone, vinylene carbonate, succinonitrile, LiBOB, LiODFB.
7. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, described organo-silicon compound are present in described organosilicon electrolyte as additive agent electrolyte or cosolvent.
8. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, the method is applied to electrochemical energy storing device.
9. the method for organosilicon electrolyte according to claim 8 and the use of silicon based electrode material fit, it is characterized in that: described electrochemical energy storing device employs silicon based electrode material, comprise sulfenyl lithium battery, metal ion battery, metal-air cell and super capacitor.
10. the method for organosilicon electrolyte according to claim 1 and the use of silicon based electrode material fit, it is characterized in that, the method is applied to lithium ion battery.
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Also Published As
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| CN107732304A (en) | 2018-02-23 |
| WO2017113473A1 (en) | 2017-07-06 |
| CN107732304B (en) | 2020-07-24 |
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