CN106935801A - A kind of non-aqueous electrolyte for lithium ion cell, lithium ion battery negative and the lithium ion battery comprising the negative pole - Google Patents
A kind of non-aqueous electrolyte for lithium ion cell, lithium ion battery negative and the lithium ion battery comprising the negative pole Download PDFInfo
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention proposes a kind of silicon cathode lithium ion battery nonaqueous electrolytic solution, lithium ion battery negative and the lithium ion battery comprising the negative pole, the nonaqueous electrolytic solution includes lithium salts, nonaqueous solvents and film for additive, and the film for additive is the silane of structure shown in formula (1)：Formula (1)；Wherein M is the alkyl C of chainn1H2n1+1, R1, R2, R3 be identical, is Cl, F, chain alkoxy Cn2H2n2+1O, amino H2N(CH2)n3In one kind；Or M is the amino H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, is Cl, F, chain alkoxy Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.The application solves the problems, such as that film rupture occurs due to the Volumetric expansion of silicium cathode in existing lithium ion battery by the forming silane film additive of addition said structure in the electrolytic solution.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly to a kind of silicon cathode lithium ion battery nonaqueous electrolytic solution, lithium from
Sub- GND and the lithium ion battery comprising the negative pole.
Background technology
In the prior art, silica-base material（Silicon, silicon alloy and Si-C composite material）Because of the theory at room temperature with superelevation
Specific capacity and suitable operating voltage, therefore, silicium cathode in lithium ion battery of future generation as it is possible that replace graphite cathode
And receive much concern；On the other hand, silicon electrode is compared with graphite electrode, and silicon electrode Volume Changes in charge and discharge process are bigger, and
Silicon face is reactive stronger with electrolyte, and battery can still occur after being circulated by first charge-discharge on the surface of silicon electrode
The reduction reaction of electrolyte, therefore, electrode surface covers incomplete situation in no SEI passivating films or SEI passivating films
Under, these reactions can aggravate the loss of electrode specific capacity.
And according to further investigation revealed that, according to silicon as negative electrode active material, lithium salts in silicon and electrolyte
Anion（Such as PF6 −）Between reaction than its with lithium battery electrolytes in organic solvent（Such as ethylene carbonate（EC）, carbonic acid
Diethylester（DEC）Deng）Between it is reactive stronger；The anion of the lithium salts in silicon and electrolyte（Such as PF6 −）Between react and can give birth to
Into the phosphorus fluorine compounds of stabilization, and the silicon electrode covered by these phosphorus fluorine compounds just can not react with lithium again, so as to cause
The decline of battery specific capacity；Therefore, in order to prevent the direct reaction between silicon electrode and electrolyte, to electrode/organic electrolyte
SEI layers modified seems particularly necessary between interface.
Current most of researchers still by adding vinylene carbonate in the electrolytic solution（VC）Or other film forming
Additive is used as silicium cathode film for additive, and the film forming mechanism of such film for additive is roughly the same, is by certain
Current potential issues raw reduction reaction and is forming layer protecting film in negative pole；Such method there is a problem of one it is larger because silicon
Negative pole lithium ion it is embedding de- during apparent volumetric expansion can occur, this allows for the diaphragm formed in negative terminal surface
Ruptured because of the volumetric expansion of silicon, in the charge and discharge process that lithium battery carries out next time, the local meeting of protection film rupture
There is side reaction with electrolyte and consume electrolyte, vicious circle is formed with this.
The content of the invention
The present invention is directed to above-mentioned technical problem, includes present applicant proposes a kind of silicon cathode lithium ion battery nonaqueous electrolytic solution
Lithium salts, nonaqueous solvents and film for additive, it is characterised in that the film for additive is the silane of structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, be-Cl ,-F, l chains alkoxy-
Cn2H2n2+1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical,
It is-Cl ,-F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3
≤15。
The application passes through to add the forming silane film additive of herein described structure in the electrolytic solution, the silane of the structure into
Film additive belongs to a kind of long-chain macromolecule, and easily adsorbs in silicium cathode material surface, the Si- in this kind of silane of structure
R1、Si-R2、Si-R3Key easily occurs to hydrolyze and form Si -- H bond；At the same time, silicium cathode material layer in atmosphere when easily occur
Hydroxylating, Si-OH keys are formed on surface, and when surface, to form a large amount of Si-OH keys silicium cathode material layers non-aqueous with described herein
During electrolyte contacts, the forming silane film additive of herein described structure is adsorbed on the surface of silicium cathode material layer, after hydrolysis
Forming silane film additive molecule in Si -- H bond and hydroxylating after the Si-OH keys of silicium cathode material surface that polycondensation occurs is anti-
The bonding connection of Si-O-Si keys, the Si-R in the forming silane film additive molecule should be formed1、Si-R2、Si-R3Key is by Si-O-Si keys
Instead of so as to form close-packed arrays, sequential 2 D and single point of thermodynamically stable silane self assembly in silicium cathode material surface
Sub- film layer；The unimolecule film layer can effectively prevent solvent molecule from passing through, and by solvent molecule isolation near silicium cathode, so that
Prevent solvent molecule that reduction reaction occurs in negative terminal surface；Also, when there is Volumetric expansion in silicium cathode, the list film layer
State can be remained intact on silicium cathode surface, effectively hinder contact of the silicium cathode with electrolyte, solved in the prior art
There is the problem of film rupture due to the Volumetric expansion of silicium cathode after silicium cathode surface filming in common film for additive.
The application further provides for a kind of silicium cathode, including negative current collector and the silicium cathode positioned at negative current collector surface
Material layer, it is characterised in that described also including the film for additive self-assembled monolayer layer positioned at silicium cathode material surface
Film for additive is the silane of structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, be-Cl ,-
F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
The forming silane film additive of the structure is adsorbed in silicium cathode material surface, is formed tightly in silicium cathode material surface
Solid matter row, sequential 2 D and thermodynamically stable silane self-assembled monolayer layer, can occur volumetric expansion effect in silicium cathode
At once, silicium cathode surface is remained intact state, prevent the problem of film rupture due to the Volumetric expansion of silicium cathode.
Present invention further proposes a kind of preparation method of silicium cathode, including：
(1) silicium cathode material layer is formed on negative current collector surface；
(2) the above-mentioned nonaqueous electrolytic solution of the application is contacted with silicium cathode material surface, the temperature of contact is 20 ~ 50 DEG C, is connect
The time of touching is 24h ~ 96h.
Present invention further proposes a kind of silicium cathode prepared by above-mentioned silicium cathode preparation method.By this kind of side
The silicium cathode that method is prepared, effectively can form one layer of silane of the herein described structure of stabilization on the surface of silicium cathode
Film for additive self-assembled monolayer layer, the unimolecule film layer can not only effectively by the solvent molecule isolation in electrolyte
Near negative pole, there is side reaction with negative terminal surface to prevent solvent molecule, meanwhile, the unimolecule film layer will not be because of silicium cathode
Volumetric expansion and the problem that ruptures, when silicium cathode occurs Volumetric expansion, the unimolecule film layer can be still
The state for remaining intact, effectively to prevent solvent molecule from influenceing battery performance there is reduction reaction on silicium cathode surface.
Present invention further proposes a kind of silicon cathode lithium ion battery, including housing and be contained in housing battery core,
Nonaqueous electrolytic solution, battery core includes positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterised in that the negative pole is
Above-mentioned any one silicium cathode for being provided.The lithium ion battery negative that the application is provided, with good cycle performance and compared with
Efficiency for charge-discharge high.
Silicium cathode of the invention can after above-mentioned electrolyte is applied to battery, be formed after film for additive and cathode contact
The silicium cathode of attachment self-assembled monolayer layer, it is also possible to which the formation that outside batteries etc. are directly prepared has self-assembled monolayer layer
Silicium cathode, after be applied to battery, present invention protection is a kind of film for additive with special construction in containing silicium cathode
Battery in application.
Specific embodiment
The present invention proposes a kind of silicon cathode lithium ion battery nonaqueous electrolytic solution, including lithium salts, nonaqueous solvents and film forming
Additive, the film for additive is the silane of structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, be-Cl ,-
F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that M in structure above for chain alkyl-
Cn1H2n1+1, R1, R2, R3 be identical, is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤20,1≤n2
≤4。
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that M in structure above for chain alkyl-
Cn1H2n1+1, R1, R2, R3 be identical, is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤10,1≤n2
≤4。
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that the film for additive is six alkyltrichlorosilanes, ten alkane
One kind in base trichlorosilane, octadecyl trichlorosilane alkane, hexadecyl trimethoxy silane, octadecyltriethoxy silane
Or it is various.
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 phase
Together, it is chain alkoxy -Cn2H2n2+1O, wherein, 3≤n1 ＇≤20,1≤n2≤4.
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that the film for additive is 3- aminopropyl trimethoxies
One or two in silane or 11- amino-undecanoic base trimethoxy silanes.
According to nonaqueous electrolytic solution proposed by the present invention, it is preferable that described on the basis of the gross weight of the nonaqueous electrolytic solution
The content of film for additive is 0.1% ~ 10%；Present inventor is had found by numerous experiments, when the film for additive
Account for nonaqueous electrolytic solution gross mass 0.1% ~ 10% when, form self-assembled monolayer layer excellent effect, and will not be to battery
Other performances are impacted.
According to non-aqueous electrolyte for lithium ion cell proposed by the present invention, in lithium ion battery non-aqueous solution electrolysis of the present invention
In liquid, nonaqueous solvents is not particularly limited, the various nonaqueous solvents that can be commonly used using those skilled in the art, for example
At least one in carboxylic acid esters solvent, carbonate-based solvent, nitrile solvents or ketones solvent can be selected from；Under preferable case,
The nonaqueous solvents is selected from methyl ethyl carbonate（EMC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）, ethylene carbonate
(EC), propene carbonate (PC), butylene (BC), ethylene sulfite（ES）, propylene sulfite（PS）, sulfurous acid two
Ethyl ester（DES）, gamma-butyrolacton（BL）, dimethyl sulfoxide (DMSO) (DMSO), ethyl acetate, one or more in methyl acetate；Enter one
Preferably, the nonaqueous solvents is selected from the carbon such as methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC) to step
One or more in acid esters；Preferably, the nonaqueous solvents is methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), carbonic acid
The mixing of diethylester (DEC) three, and the mass ratio of each material meets methyl ethyl carbonate (EMC)：Dimethyl carbonate (DMC)：Carbon
Diethyl phthalate (DEC)=2：1：3~2：3：1.
According to non-aqueous electrolyte for lithium ion cell proposed by the present invention, the lithium salts for those skilled in the art commonly use it is each
Lithium salts is planted, for example, can be selected from lithium hexafluoro phosphate（LiPF6）, lithium chlorate（LiClO4）, LiBF4（LiBF4）, hexafluoroarsenate
Lithium（LiAsF6）, lithium perchlorate, hexafluorosilicic acid lithium（LiSiF6）, tetrachloro-lithium aluminate（LiAlCl4）, double second dioxalic acid lithium borates
（LiBOB）, difluorine oxalic acid boracic acid lithium（LiODFB）, lithium chloride（LiCl）, lithium bromide（LiBr）, lithium iodide（LiI）, fluoroform
Sulfonic Lithium（LiCF3SO3）, it is double（Trifluoroacetyl group）Inferior amine salt（Li(CF3CO2)2N）, it is double（Trimethyl fluoride sulfonyl）Imine lithium（Li
(CF3SO2)2N）Or it is double（Pentafluoroethyl group sulphonyl）Imine lithium（Li(SO2C2F5)2N）In one or more, the concentration of lithium salts is this
The conventional concentration in field, with weight percentage, the weight of lithium salts is the 8.5-18.5wt% of the electrolyte gross weight, preferably feelings
Under condition, the present invention uses LiPF6Used as lithium salts, its concentration is 8.5-18.5wt%, preferably 10-16wt%.
The preparation method of the non-aqueous electrolyte for lithium ion cell that the present invention is provided, is the conventional side of those skilled in the art
Method, will each component（Including lithium salts, nonaqueous solvents and film for additive）Well mixed, mode and order to mixing are originally
Invention is not particularly limited；Under preferable case, each component (including lithium salts, nonaqueous solvents, various additives) is blended in argon
Carried out in gas gloves；Currently preferred method is that lithium salts is dissolved in nonaqueous solvents in argon gas glove box, is subsequently adding
First additive of the present invention or the first additive and the mixing of Second addition, that is, obtain nonaqueous electrolytic solution.
Born present invention further proposes a kind of silicium cathode, including negative current collector and the silicon positioned at negative current collector surface
Pole material layer, it is characterised in that also including the film for additive self-assembled monolayer layer positioned at silicium cathode material surface, institute
State the silane that film for additive is structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, be-Cl ,-
F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
In accordance with the present invention it is preferred that, in above-mentioned silicium cathode, M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, be-
Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤20,1≤n2≤4；It is further preferred that above-mentioned silicon is negative
In the lithium ion battery negative of pole, M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, be-Cl or chain alkoxy-
Cn2H2n2+1One kind in O, wherein, 3≤n1≤10,1≤n2≤4；It is further preferred that the film for additive is six alkane
Base trichlorosilane, ten alkyltrichlorosilanes, octadecyl trichlorosilane alkane, hexadecyl trimethoxy silane, the second of octadecyl three
One or more in TMOS.
In accordance with the present invention it is preferred that, in above-mentioned silicium cathode, M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical,
It is chain alkoxy -Cn2H2n2+1O, wherein, 3≤n1 ＇≤20,1≤n2≤4；Preferably, the film for additive is 3- amino
One or two in propyl trimethoxy silicane or 11- amino-undecanoic base trimethoxy silanes.
The invention allows for a kind of preparation method of silicium cathode, including：
(1) silicium cathode material layer is formed on negative current collector surface；
(2) the above-mentioned nonaqueous electrolytic solution of the application is contacted with silicium cathode material surface, the temperature of contact is 20 ~ 50 DEG C, is connect
The time of touching is 24h ~ 96h.
In the negative preparation method of the silicon, the method for forming silicium cathode material layer on negative current collector surface in step (1) is
The existing conventional method for preparing silicium cathode material layer on negative current collector surface, the application is not particularly limited, including will be negative
Pole active material silicon, cathode conductive agent, negative electrode binder and organic solvent are mixed to get cathode size, and cathode size is coated on
Negative current collector surface, silicium cathode material layer is formed on negative current collector surface；The application leads to negative electrode active material silicon, negative pole
Electric agent, negative electrode binder, without particular/special requirement, are that the conventional negative electrode active material silicon in this area, cathode conductive agent, negative pole glue
Knot agent；For example, negative electrode active material silicon can be the conventional silicium cathode in this area；Negative electrode binder can routinely make for this area
Negative electrode binder；Cathode conductive agent can be cathode conductive agent commonly used in the art；Negative current collector is this area
Negative current collector known to technical staff, for example, Copper Foil；The silicium cathode material layer for preparing is that the conventional silicon in this area is born
Pole material layer, needs not move through specially treated；When silicium cathode material is placed in air, easily there is hydroxylating and formed largely on surface
Si-OH keys；The silicium cathode material layer in step (1) is contacted with nonaqueous electrolytic solution described herein in above-mentioned steps (2)
During, as long as ensure temperature at 20 ~ 50 DEG C, and time of contact is 24h ~ 96h, as long as way of contact satisfaction can
It is fully contacted with by the application nonaqueous electrolytic solution and silicium cathode material surface, for example, can is by positive plate, negative plate
And battery diaphragm encapsulation is in the cell housing, after nonaqueous electrolytic solution described herein is injected in the housing, obtains battery laggard
Row ageing, Aging Temperature is 20 ~ 50 DEG C, and preferably 35 DEG C, digestion time is 24h ~ 96h, is completed during this herein described
Nonaqueous electrolytic solution and silicium cathode material surface be fully contacted.Contain the application institute in nonaqueous electrolytic solution described herein
The forming silane film additive of structure is stated, after nonaqueous electrolytic solution described herein is injected in battery container, now silicium cathode
Material surface has been formed with substantial amounts of Si-OH keys, and the forming silane film of the herein described structure contained in nonaqueous electrolytic solution
Si-R in additive1、Si-R2、Si-R3Key easily occurs to hydrolyze and form Si -- H bond, and nonaqueous electrolytic solution is injected in battery container
Afterwards, nonaqueous electrolytic solution is fully contacted with silicium cathode material surface, and the forming silane film additive in nonaqueous electrolytic solution is adsorbed in silicon
The surface of negative electrode material layer, in forming silane film additive molecule through the Si -- H bond after hydrolysis and silicium cathode material surface
The bonding connection of Si-O-Si keys, the Si-R in the forming silane film additive molecule formed and polycondensation reaction in Si-OH keys there is1、Si-R2、
Si-R3Key is replaced by Si-O-Si keys, thus this kind of forming silane film additive molecule of structure can be formed closely on silicium cathode surface
Arrangement, sequential 2 D and thermodynamically stable self-assembled monolayer layer；The unimolecule film layer can effectively prevent solvent molecule
Pass through, and by solvent molecule isolation near silicium cathode, so as to prevent solvent molecule that reduction reaction occurs in negative terminal surface；And
And, when silicium cathode occurs Volumetric expansion, the list film layer can remain intact state, effective ground resistance on silicium cathode surface
Hinder contact of the silicium cathode with electrolyte, solve in the prior art common film for additive after silicium cathode surface filming due to silicon
The Volumetric expansion of negative pole and there is the problem of film rupture.
Present invention further proposes a kind of lithium ion battery silicium cathode prepared by above-mentioned silicium cathode preparation method,
The silicon cathode lithium ion battery silicium cathode prepared by the above method, effectively can form on the surface of silicium cathode material layer
One layer of forming silane film additive self-assembled monolayer layer of the herein described structure of stabilization, the effective silicium cathode that solves is because of body
The problem that product expansion ruptures.
The application further provides a kind of silicon cathode lithium ion battery, including housing and be contained in housing battery core,
Nonaqueous electrolytic solution, battery core includes positive pole, negative pole and the barrier film between positive pole and negative pole, and the negative pole is what the application was proposed
Any silicium cathode.
According to the present invention, further, film for additive is contained in the nonaqueous electrolytic solution, the film for additive is formula
(1) silane of structure shown in：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, is-Cl ,-F, chain
Shape alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
The application does not have special limitation to other the Nomenclature Composition and Structure of Complexes of lithium ion battery, and positive pole therein includes positive pole collection
Fluid and the positive electrode positioned at plus plate current-collecting body surface, the positive electrode include positive active material, positive conductive agent,
Positive electrode binder, the positive active material, positive conductive agent, positive electrode binder can be that positive pole commonly used in the art is lived
Property material, positive conductive agent, positive electrode binder, it is preferable that the positive active material be LiNi0.5Mn1.5O4、LiNi1- xMnxO2、LiNi1-xCoxO2、LiNi1-y-z CoyMnzO2、LiNi1-y-z CoyAlzO2In one or more, wherein, 0≤x≤1, y
>=0, z >=0, y+z≤1；The positive conductive agent is one or more in acetylene black, CNT, the positive electrode binder
It is Kynoar；Negative pole is any negative pole provided herein；The membrane layer be it is commonly used in the art every
Film layer.
The method that what the preparation method of lithium ion battery of the invention was known in the art prepare lithium battery, such as including will
(negative pole refers to not in silicium cathode material surface formation forming silane film additive self assembly list for the positive pole for preparing and negative pole
The negative pole of molecule film layer) between barrier film is set, winding or constitute battery core after folding, the battery core is contained in battery case, note
Enter nonaqueous electrolytic solution described herein, battery case sealing ageing then be can be prepared by into lithium ion battery, will be herein described
Nonaqueous electrolytic solution injection battery container and complete nonaqueous electrolytic solution described herein and silicium cathode material after sealing ageing
The contact of layer surface, during this, the forming silane film additive of herein described structure is adsorbed on the surface of silicium cathode material layer
Form self-assembled monolayer layer；The method and steps of the ageing of lithium ion battery is well known to those skilled in the art, herein
Do not repeat, the temperature of lithium ion battery ageing is 20 ~ 50 DEG C, and preferably 35 DEG C, the time of ageing is 48h；In ageing process,
Forming silane film additive in nonaqueous electrolytic solution is adsorbed in silicium cathode material surface and forms silane self-assembled monolayer layer,
This kind of unimolecule film layer close-packed arrays, sequential 2 D and Thermodynamically stable, can effectively alleviate silicium cathode because volumetric expansion triggers
Problem and isolation silicium cathode and electrolyte between contact；
In the application, the preparation method of battery can also be and first prepare in silicium cathode material surface formation forming silane film
The negative pole of additive self-assembled monolayer layer, specific method is to form silicium cathode material on the surface of negative current collector such as Copper Foil
After the bed of material, then non-aqueous solution electrolysis liquor described herein and silicium cathode material layer are fully contacted, specific contact temperature
It is 20 ~ 50 DEG C to spend, preferably 35 DEG C, and time of contact is 24h ~ 96h, preferably 48h；Contact method can be it is any so that
The forming silane film additive absorption of herein described structure can for example be coated with silicon in the method for silicium cathode material surface
The negative current collector of negative electrode material layer is soaked in nonaqueous electrolytic solution described herein, is 20 ~ 50 DEG C by soaking temperature, immersion
Time is 24h ~ 96h；Can also be that the negative current collector for being coated with silicium cathode material layer is soaked in other and contains the application institute
In stating the liquid of forming silane film additive of structure, or other cause that the forming silane film additive of herein described structure is adsorbed
Method of the silane self-assembled monolayer layer without other performances of influence silicium cathode material layer is formed in silicium cathode material surface,
The application is not particularly limited, as long as being so that the forming silane film additive of herein described structure is adsorbed in silicium cathode material layer
Surface simultaneously forms self-assembled monolayer layer, and the process is not impacted to other performances of silicium cathode material layer.Then
The negative of the forming silane film additive self-assembled monolayer layer of herein described structure will be formed in silicium cathode material surface
Barrier film is set between pole, positive pole, battery core is constituted after winding or folding, the battery core is contained in battery case, in battery container
Middle injection any nonaqueous electrolytic solution well known in the art, the nonaqueous electrolytic solution can be non-aqueous solution electrolysis described herein
Liquid, it is also possible to be free from the nonaqueous electrolytic solution of the forming silane film additive of herein described structure, if can be used for lithium from
Nonaqueous electrolytic solution in sub- battery.
The lithium ion battery negative that the application is provided, with good cycle performance and efficiency for charge-discharge higher.
With reference to embodiments the lithium to non-aqueous electrolyte for lithium ion cell of the invention and containing the nonaqueous electrolytic solution from
Sub- battery is described further.
Embodiment 1
(1) preparation of nonaqueous electrolytic solution：
By ethylene carbonate, diethyl carbonate, dimethyl carbonate by proportioning 2 in argon gas glove box：1：3 are made into 100 weight portions
Nonaqueous solvents, then by the LiPF of 12 weight portions6It is dissolved in the above-mentioned nonaqueous solvents for preparing, is subsequently adding the chain of 3 weight portions
Six alkyltrichlorosilanes (wherein M is the alkyl of chain six, and R1, R2, R3 are identical, are-Cl) of shape；Obtain the lithium of the present embodiment from
Sub- battery nonaqueous electrolytic solution, is designated as C1；
（2）The preparation of silicon cathode lithium ion battery：
By negative electrode active material silicon, contracting methylcellulose (CMC), butadiene-styrene rubber (SBR) by proportioning 100： 3：2 are well mixed
After suppress on Copper Foil, forming surface has the copper foil current collector of silicium cathode material layer, and the surface is had into silicium cathode material layer
Copper foil current collector as negative plate；Using metal lithium sheet as positive plate；With PE/PP composite diaphragms as amberplex, use
The nonaqueous electrolytic solution C1 of the present embodiment, button cell S1 is made using this area conventional method.
Embodiment 2
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Step uses 3 in (1)
The ten alkyltrichlorosilanes film for additive (wherein M is the alkyl of chain ten, and R1, R2, R3 are identical, are-Cl) of weight portion replace chain
Six alkyltrichlorosilanes of shape, prepare non-aqueous electrolyte for lithium ion cell C2 and button cell S2.
Embodiment 3
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Step uses 3 in (1)
Octadecyl trichlorosilane alkane film for additive (wherein M is chain octadecyl, and R1, R2, R3 are identical, the are-Cl) generation of weight portion
For six alkyltrichlorosilanes of chain, non-aqueous electrolyte for lithium ion cell C3 and button cell S3 is prepared.
Embodiment 4
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Step uses 3 in (1)
Weight portion 3- TSL 8330s film for additive (wherein M is chain 3- aminopropyls, and R1, R2, R3 be identical,
It is CH3O) replace six alkyltrichlorosilanes of chain, prepare non-aqueous electrolyte for lithium ion cell C4 and button cell S4.
Embodiment 5
（1）The preparation of silicium cathode
Prepare non-aqueous solution electrolysis liquor：By ethylene carbonate, diethyl carbonate, dimethyl carbonate by proportioning in argon gas glove box
2：1：3 are made into 100 weight portion nonaqueous solvents, then by the LiPF of 12 weight portions6It is dissolved in the above-mentioned nonaqueous solvents for preparing, so
Six alkyltrichlorosilanes (wherein M is the alkyl of chain six, and R1, R2, R3 are identical, are-Cl) of the chain of 3 weight portions are added afterwards, are obtained
To non-aqueous solution electrolysis liquor；By negative electrode active material silicon, contracting methylcellulose (CMC), butadiene-styrene rubber (SBR) by proportioning 100：
3：2 it is well mixed after suppress on Copper Foil, forming surface there is the copper foil current collector of silicium cathode material layer；The surface is had
The copper foil current collector of silicium cathode material layer is soaked in above-mentioned non-aqueous solution electrolysis liquor, and soak time is 48h, and soaking temperature is 35
DEG C, prepare silicon cathode lithium ion battery negative plate A1；
（2）The preparation of nonaqueous electrolytic solution
By ethylene carbonate, diethyl carbonate, dimethyl carbonate by proportioning 2 in argon gas glove box：1：3 are made into 100 weight portions
Nonaqueous solvents, then by the LiPF of 12 weight portions6It is dissolved in the above-mentioned nonaqueous solvents for preparing, obtains the lithium ion of the present embodiment
Battery nonaqueous electrolytic solution, is designated as C11；
（3）With step（1）In A1 be negative plate, using metal lithium sheet as positive plate；With PE/PP composite diaphragms as ion exchange
Film, using the nonaqueous electrolytic solution C11 of the present embodiment, button cell S11 is made using this area conventional method.
Embodiment 6
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 7, difference is：Step uses 3 in (1)
The ten alkyltrichlorosilanes film for additive (wherein M is the alkyl of chain ten, and R1, R2, R3 are identical, are-Cl) of weight portion replace chain
Six alkyltrichlorosilanes of shape, prepare silicon cathode lithium ion battery negative plate A2 and button cell S12.
Embodiment 7
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 7, difference is：Used in step (1)
The octadecyl trichlorosilane alkane film for additive (wherein M is chain octadecyl, and R1, R2, R3 are identical, are-Cl) of 3% weight portion
Instead of six alkyltrichlorosilanes of chain, silicon cathode lithium ion battery negative plate A3 and button cell S13 is prepared.
Embodiment 8
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 7, difference is：Step uses 3 in (1)
(wherein M is chain 3- aminopropyls, R1, R2, R3 to the 3- TSL 8330 forming silane films additive of weight portion
It is identical, it is CH3O silicon cathode lithium ion battery negative plate A4 and button) are prepared instead of six alkyltrichlorosilanes of chain
Battery S14.
Embodiment 9
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Used in step (1)
The hexadecyl trimethoxy silane of 0.112 weight portion replaces six alkyltrichlorosilanes of chain, prepares lithium ion battery
Nonaqueous electrolytic solution C5 and button cell S5.
Embodiment 10
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Used in step (1)
The 11- amino-undecanoic bases trimethoxy silane of 1.12 weight portions replace chain six alkyltrichlorosilanes, prepare lithium from
Sub- battery nonaqueous electrolytic solution C6 and button cell S6.
Embodiment 11
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：Step uses 6 in (1)
The octadecyltriethoxy silane of weight portion replaces six alkyltrichlorosilanes of chain, prepares the non-water power of lithium ion battery
Solution liquid C7 and button cell S7.
Comparative example 1
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 1, difference is：In step (1) not
Six alkyltrichlorosilanes are added, nonaqueous electrolytic solution DC1 and button cell DS1 is prepared.
Comparative example 2
Nonaqueous electrolytic solution and button cell are prepared using step same as Example 5, difference is：In step (1) not
Six alkyltrichlorosilanes are added, silicon cathode lithium ion battery negative plate DA1 and button cell DS11 is prepared.
Performance test
（1）Unimolecule film layer is tested
Test philosophy：Monomolecular film is a class hydrophobic group due to disconnected end group, therefore can apply contact angle measurement
Detected, its principle is that, by wetting, the process for generally being replaced solid gas interface by solid liquid interface turns into wetting, specially
By liquid drop on a solid surface, because property is different, some meeting drawouts, what is had is then attached on surface as flat convex lens shape
Mirror, this phenomenon is referred to as wetting action, and the size of degree of wetting is generally judged with contact angle, and its degree of wetting is big, contact
Angle θ is small, and degree of wetting is small, then contact angle θ is big, and general θ is then nonwetting more than 90 degree.If silicium cathode surface do not formed one layer with
Hydrophobic group is the self-assembled monolayer layer of end group, and its surface is then for hydrophobic, therefore silicium cathode table of the water droplet after film forming
The contact angle θ in face should be increase than the silicium cathode without film forming；Measure the contact of each embodiment comparative example silicium cathode piece
Angle size is shown in Table 1.
（2）Specific capacity test under battery high pressure：
Each experimental cell S1-S6, S11-S16, DS1-DS2 are carried out into constant current charge extremely with the electric current of 0.1C at normal temperatures
Blanking voltage is 4.9V, with identical current discharge to 3.0V, records charge/discharge capacity, the results are shown in Table 2.
（3）Circulating battery is tested
Battery S1-S6, S11-S16, DS1-DS2 are loaded on secondary cell ability meter BS-9300 in correct method, first
With 1C constant-current constant-voltage chargings to 4.9V, shelve 5 minutes, 3.0V is discharged to 1C, then with 1C constant-current constant-voltage chargings to 4.9V, with regard to this
Sample is circulated 100 times.After circulation terminates, treat that battery temperature recovers normal temperature, it is fully charged with 1C, then 3.0V is discharged to 0.2C, draw
Residual capacity, capability retention is obtained final product by residual capacity divided by circulation volume first, the results are shown in Table 2.
Table 1
Table 2
As can be seen from Table 1, it is 90 °, comparative example to the contact angle of water without the fresh silicium cathode piece of any treatment
In silicium cathode piece to the contact angle of water also close to 90 °, and in the embodiment of the present application provide silicium cathode piece, to the contact angle of water
90 ° are far longer than, the silicium cathode piece that the application is provided is illustrated, the forming silane film additive absorption of herein described structure is negative in silicon
The surface of pole material layer forms self-assembled monolayer layer.
As can be seen from Table 2, the silicium cathode that the nonaqueous electrolytic solution of the application and the application are provided is applied to lithium-ion electric
Pond, in the case where original charge/discharge capacity and efficiency for charge-discharge is kept, the cycle performance of battery obtains very big carrying to battery
Rise, the battery that the embodiment of the present application is provided is far longer than comparative example in the capability retention minimum 70% after 100 circulate
22%, the silicium cathode that the nonaqueous electrolytic solution of the application and the application are provided is applied to lithium ion battery, can greatly lift battery
Cycle performance.
Claims (17)
1. a kind of silicon cathode lithium ion battery nonaqueous electrolytic solution, including lithium salts, nonaqueous solvents and film for additive, its feature exist
In the film for additive is the silane of structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, be-Cl ,-
F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that M is the alkyl-C of chainn1H2n1+1, R1, R2, R3
It is identical, it is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤20,1≤n2≤4.
3. nonaqueous electrolytic solution according to claim 2, it is characterised in that M is the alkyl-C of chainn1H2n1+1, R1, R2, R3
It is identical, it is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤10,1≤n2≤4.
4. nonaqueous electrolytic solution according to claim 3, it is characterised in that the film for additive is six alkyl trichlorine silicon
Alkane, ten alkyltrichlorosilanes, octadecyl trichlorosilane alkane, hexadecyl trimethoxy silane, octadecyltriethoxy silane
In one or more.
5. nonaqueous electrolytic solution according to claim 1, it is characterised in that M is the amino-H of chain2N(CH2)N1 ＇, R1, R2,
R3 is identical, is chain alkoxy -Cn2H2n2+1O, wherein, 3≤n1 ＇≤20,1≤n2≤4.
6. nonaqueous electrolytic solution according to claim 5, it is characterised in that the film for additive is 3- aminopropyl front threes
One or two in TMOS or 11- amino-undecanoic base trimethoxy silanes.
7. nonaqueous electrolytic solution according to claim 1, it is characterised in that the gross weight with the nonaqueous electrolytic solution is as base
Standard, the content of the film for additive is 0.1% ~ 10%.
8. a kind of silicium cathode, including negative current collector and the silicium cathode material layer positioned at negative current collector surface, it is characterised in that
Also include the film for additive self-assembled monolayer layer positioned at silicium cathode material surface, the film for additive is formula (1)
The silane of shown structure：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, chain amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, be-Cl ,-
F, chain alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
9. silicium cathode according to claim 8, it is characterised in that M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical,
It is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤20,1≤n2≤4.
10. negative pole according to claim 9, it is characterised in that M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical,
It is-Cl or chain alkoxy -Cn2H2n2+1One kind in O, wherein, 3≤n1≤10,1≤n2≤4.
11. negative poles according to claim 10, it is characterised in that the film for additive is six alkyltrichlorosilanes, ten
In alkyltrichlorosilanes, octadecyl trichlorosilane alkane, hexadecyl trimethoxy silane, octadecyltriethoxy silane one
Plant or various.
12. negative poles according to claim 8, it is characterised in that M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 phase
Together, it is chain alkoxy -Cn2H2n2+1O, wherein, 3≤n1 ＇≤20,1≤n2≤4.
13. negative poles according to claim 12, it is characterised in that the film for additive is 3- aminopropyl trimethoxies
One or two in silane or 11- amino-undecanoic base trimethoxy silanes.
A kind of 14. preparation methods of silicium cathode, including：
(1) silicium cathode material layer is formed on negative current collector surface；
(2) nonaqueous electrolytic solution described in claim 1-7 any one is contacted with silicium cathode material surface, the temperature of contact
It it is 20 ~ 50 DEG C, time of contact is 24h ~ 96h.
15. a kind of silicium cathodes, it is characterised in that the silicium cathode is prepared as the method described in claim 14.
A kind of 16. silicon cathode lithium ion batteries, including housing and battery core, the nonaqueous electrolytic solution being contained in housing, battery core include
Positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterised in that the negative pole is claim 8-15 any one
The silicium cathode of offer.
17. silicon cathode lithium ion batteries according to claim 16, it is characterised in that contain into the nonaqueous electrolytic solution
Film additive, the film for additive is the silane of structure shown in formula (1)：
Formula (1)；Wherein M is the alkyl-C of chainn1H2n1+1, R1, R2, R3 be identical, is-Cl ,-F, chain alkoxy -Cn2H2n2+ 1O, amino-H2N(CH2)n3In one kind；Or M is the amino-H of chain2N(CH2)N1 ＇, R1, R2, R3 be identical, is-Cl ,-F, chain
Shape alkoxy -Cn2H2n2+1One kind in O；Wherein, 1≤n1≤20,3≤n1 ＇≤20,1≤n2≤4,2≤n3≤15.
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Application publication date: 20170707 |