CN109921092A - A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte - Google Patents
A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion, disclose a kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte.Silicon-based anode non-aqueous electrolyte for lithium ion cell of the invention includes electrolyte lithium salt, non-aqueous organic solvent and film for additive, containing silicon base compound and/or conventional anode film for additive shown in formula (I) structure in the film for additive, while invention additionally discloses a kind of silicon-based anode lithium ion batteries.Silicon substrate class additive in the present invention can form one layer of uniform flexible protective film on silicon based anode material surface; electrolyte is reduced in the oxidation reaction on battery material surface, promotes normal-temperature circulating performance, high temperature cyclic performance and the high-temperature storage performance of silicon-based anode lithium ion battery.
Description
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and
The silicon-based anode lithium ion battery of the electrolyte.
Background technique
Lithium ion battery is due to high working voltage, high-energy density, long-life, wide operating temperature range and environment friend
The advantages that good, is widely used in the fields such as 3C digital product, electric tool, electric car.In recent years, with global economy
High speed development, mobile electronic device is especially lighter, thinner smart phone enters eruptive growth therewith, and people are to lithium ion
More stringent requirements are proposed for the energy density of battery.
The energy density of lithium ion battery is improved, currently used method has: 1. improving the operating voltage of positive electrode, with
And the problem come is that on positive electrode surface oxygenolysis occurs for partial solvent under high voltage in electrolyte or additive, make
The service life of lithium ion battery greatly shortens；2. using more high discharge capacity silica-base material (the theoretical gram volume of silicon are as follows:
4200mAh/g, the theoretical gram volume of graphite are as follows: 372mAh/g).
However, compared with carbon based negative electrodes material, silica-base material have the defects that it is apparent, if silica-base material is in room temperature or height
There are huge bulk effects in warm cyclic process, on the one hand will lead to negative electrode tab expansion and cause between negative electrode material and collector
Cementability is deteriorated；On the other hand, the expansion of silicon substrate will lead to the SEI film on cathode interface and occur to break during circulating battery
It splits and recombinates, and then lead to the reduction decomposition of electrolyte, the aggravation of by-product generates, and deteriorates cycle performance of battery.
In order to solve the problems, such as that silicon based anode material is applied, from electrolyte angle, current research is main
It concentrates on developing on novel suitable additive and solvent.Common additive such as fluorinated ethylene carbonate (FEC), although very big
The chemical property of silicon-based anode lithium ion battery can be improved in degree, but excessive FEC is added and will cause battery high-temperature
The deterioration of performance, the few room temperature cycles performance that will affect battery again of additional amount.Current commercialized silicon-based anode lithium ion battery
Electrolyte also prematurity, develop new film for additive solve the above problems it is very urgent.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of above-mentioned background technique, a kind of silicon-based anode lithium ion battery is provided
Nonaqueous electrolytic solution and silicon-based anode lithium ion battery containing the electrolyte, in the electrolyte additive have good cathode at
Film properties can effectively solve normal-temperature circulating performance, high temperature cyclic performance and the high-temperature storage performance of silicon-based anode lithium ion battery
Poor problem.
To achieve the goals above, silicon-based anode non-aqueous electrolyte for lithium ion cell of the invention include electrolyte lithium salt,
Non-aqueous organic solvent and film for additive contain silicon base compound shown in formula (I) structure in the film for additive:
Wherein, R be selected from carbon atom number be 1~4 alkyl, alkenyl, alkynyl, H atom, F atom, contain fluoroalkyl and benzene
Base containing number of fluorine atoms is 0~3 on the base of middle-end containing the fluoroalkyl carbon, containing number of fluorine atoms is 0~2 on other carbon atoms.
Preferably, conventional anode film for additive, the conventional anode film forming addition are also contained in the film for additive
Agent is in vinylene carbonate (VC), fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC), 1,3- propane sulfonic acid
Ester (PS), 1,3- propylene sultones (1,3-PST), ethylene sulfite (ES), three (trimethyl silane) phosphates (TMSP),
One of three (trimethyl silane) borates (TMSB) and methane-disulfonic acid methylene ester (MMDS) are a variety of.
Preferably, the quality of the fluorinated ethylene carbonate accounts for the electrolyte gross mass
5.0%~10.0%, the quality of the vinylethylene carbonate or 1,3- propylene sultones accounts for the electrolyte
The 0.01%~1.2% of gross mass.
It is further preferred that containing vinylene carbonate, 1,3- propane sultone, fluoro carbon in the film for additive
Vinyl acetate and three (trimethyl silane) borates, or contain vinylene carbonate, 1,3- propane sultone, fluoro carbonic acid second
Enester, three (trimethyl silane) borates and vinylethylene carbonate；It is furthermore preferred that sub- containing carbonic acid in the film for additive
Vinyl acetate, 1,3- propane sultone, fluorinated ethylene carbonate and three (trimethyl silane) borates, and its additional amount is respectively
1.0%, 1.0%, 10.0%, the 1.5% of electrolyte gross mass；Or contain vinylene carbonate, 1,3- propane sultone, fluorine
For ethylene carbonate, three (trimethyl silane) borates and vinylethylene carbonate, and its additional amount is respectively the total matter of electrolyte
Amount 1.0%, 1.0%, 10.0%, 1.5%, 0.5%.
Preferably, there is silicon base compound shown in formula (I) structure to be selected from one of compound 1-6 or a variety of:
Preferably, the quality with silicon base compound shown in formula (I) structure accounts for the 0.01% of the electrolyte gross mass
~3.0%, such as 0.9%~1.1%, for another example 1%.
It is highly preferred that the quality of the film for additive accounts for the 0.5%~15.0% of the electrolyte gross mass.
Preferably, the electrolyte lithium salt is lithium hexafluoro phosphate (LiPF6), double fluorine sulfimide lithiums (LiFSi), difluoro phosphorus
Sour lithium (LiPO2F2) and one of difluorine oxalic acid boracic acid lithium (LiDFOB) or more than one mixing lithium salts, such as hexafluorophosphoric acid
The mixing lithium salts of the mixing lithium salts or lithium hexafluoro phosphate of lithium and difluorophosphate, double fluorine sulfimide lithiums and difluorophosphate,
Or the mixing lithium salts of lithium hexafluoro phosphate, difluorophosphate and difluorine oxalic acid boracic acid lithium.
Preferably, the electrolyte lithium salt additive amount accounts for the 13.0%~17.5% of the electrolyte gross mass.
It is further preferred that the electrolyte lithium salt is the mixing lithium salts of lithium hexafluoro phosphate and difluorophosphate, addition
Amount accounts for 15.0wt%, 1.0wt% of the electrolyte gross mass respectively；It or is lithium hexafluoro phosphate, double fluorine sulfimide lithiums and two
The mixing lithium salts of lithium fluophosphate, additive amount account for 15.0%, 2.0%, the 1.0% of the electrolyte gross mass respectively；It or is six
The mixing lithium salts of lithium fluophosphate, difluorophosphate and difluorine oxalic acid boracic acid lithium, additive amount account for the electrolyte gross mass respectively
15.0%, 1.0%, 1.0%.
Preferably, the non-aqueous organic solvent includes cyclic carbonate and linear carbonate, it is preferable that the cyclic carbonate
Ester is selected from one of ethylene carbonate and propene carbonate or a variety of, and the chain ester is selected from dimethyl carbonate, carbonic acid diethyl
One of ester, methyl ethyl carbonate, two (2,2,2- trifluoroethyl) carbonic esters and methyl trifluoro ethyl carbonate ester are a variety of.
Preferably, the additive amount of the cyclic carbonate accounts for the 20.0%~45.0% of the electrolyte gross mass, wherein
The additive amount of propene carbonate accounts for the 5.0%~20.0% of the electrolyte gross mass.
It is highly preferred that the non-aqueous organic solvent includes ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and carbonic acid
Vinyl acetate, diethyl carbonate and methyl ethyl carbonate 20:15:15:50 in mass ratio are mixed.
The present invention also provides a kind of silicon-based anode lithium ion battery, which includes cathode pole
Piece, anode pole piece, the isolation film being placed between cathode sheet and anode pole piece and silicon-based anode lithium-ion electric of the present invention
Pond nonaqueous electrolytic solution.
Preferably, the cathode sheet includes aluminum foil current collector and cathode diaphragm, and the anode pole piece includes copper foil afflux
Body and anode diaphragm.
Preferably, the cathode diaphragm includes cathode active material, conductive agent and binder, and the anode diaphragm includes sun
Pole active material, conductive agent and binder.
It is further preferred that the cathode active material is LiNi1-x-y-zCoxMnyAlzO2Or LiAmBnPO4, wherein 0≤x
≤ 1,0≤y≤1,0≤z≤1,0≤m≤1,0≤n≤1 and 0≤x+y+z≤1, A, B represent Fe, Mn, Co or V.
It is further preferred that the anode active material is nano-silicon, silicon alloy, SiOwThe silicon-carbon being combined with graphite
Composite material, it is preferable that the SiOwTo aoxidize sub- silicon, silica or other silica-base materials.
The present invention has the advantages that
1. cathode film formation additive (especially fluorinated ethylene carbonate) is prior to solvent in negative electrode material table in the present invention
Face reduction, forms excellent interface protective film, reduces reacting for electrode material and electrolyte；Meanwhile being formed by solid electricity
It is low to solve plasma membrane impedance, is conducive to improve inside lithium ion cell kinetic characteristics；
2. silicon substrate class additive shown in Chinese style (I) structure of the present invention can form one layer on silicon based anode material surface
Even flexible protective film reduces electrolyte in the oxidation reaction on battery material surface；Functional group containing silicon substrate in such additive
Preferentially it is embedded into negative electrode material with silicon based anode material effect, tail portion longitudinally forms a film, so that it is more tough to be formed by SEI film
Property；
3. silicon substrate class shown in cathode film formation additive (especially fluorinated ethylene carbonate) and formula (I) structure in the present invention
Additive collective effect, the risk that a degree of can be reduced FEC high temperature and produce gas, improves the high temperature cyclic performance and height of battery
Warm storage performance；The addition of other auxiliary conventional additives, can preferably modify SEI film, improve battery performance.
4. being added to the double fluorine sulfimide lithiums of novel conductive lithium salts with good filming characteristic, difluorophosphoric acid in the present invention
Lithium and difluorine oxalic acid boracic acid lithium, compare and LiPF are used alone6, it is applied in combination using various new film forming lithium salts, is conducive to change
Kind power battery high temperature performance, high rate performance, long circulating performance.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " containing " or its any other deformation, it is intended that covering non-exclusionism
Include.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those elements, but
It may include not expressly listed other elements or such composition, step, method, product or the intrinsic element of device.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
The preparation of electrolyte: in the glove box full of argon gas, by ethylene carbonate, diethyl carbonate and methyl ethyl carbonate
It is mixed in mass ratio for EC:PC:DEC:EMC=20:15:15:50, is then slowly added to 15.0wt%'s to mixed solution
The LiPO of lithium hexafluoro phosphate and 1.0wt%2F2, it is eventually adding based on silicon shown in electrolyte total weight 1.0wt% formula (I) structure
Base class compound (specific as shown in table 1), obtains the lithium-ion battery electrolytes of embodiment 1 after mixing evenly.
Embodiment 2-14 and comparative example 1-9
As shown in table 1, in embodiment 2-14 and comparative example 1-9, in addition to each ingredient composition and ratio of electrolyte is added as shown in table 1
It is other same as Example 1 outside adding.
Each ingredient composition and ratio of electrolyte of 1 embodiment 1-14 of table and comparative example 1-9
Effect example
The artificial graphite material that prepared lithium-ion battery electrolytes injection process is sufficiently dried/
LiNi0.6Co0.2Mn0.2O2In battery, battery is shelved by 45 DEG C, after high-temperature clamp chemical conversion and secondary sealing, carries out conventional point
Hold.
1) battery normal-temperature circulating performance is tested: at 25 DEG C, the battery after partial volume being charged to 4.2V by 1C constant current constant voltage, is cut
Only electric current 0.05C is recycled according to this then by 1C constant-current discharge to 2.8V, calculates the 1000th cycle after charge/discharge 1000 times circulations
Circulation volume conservation rate, calculation formula are as follows: the 1000th circulation volume conservation rate (%)=(the 1000th cyclic discharge capacity/
Cyclic discharge capacity for the first time) × 100%；
2) 60 DEG C of constant temperature storage thickness swellings and capacity surplus ratio are tested: putting battery recycled at normal temperature with 0.5C first
Charge and discharge 1 time (4.2V~2.8V), record discharge capacity C before battery storage0, then battery constant-current constant-voltage charging to 4.2V is expired
Electric state uses the thickness d before vernier caliper test battery high-temperature storage1(two diagonal lines of above-mentioned battery are distinguished by straight line
It is connected, two diagonal line crosspoints are cell thickness test point), battery is put into 60 DEG C of insulating boxs stores 7 days later, deposited
Battery is taken out after the completion of storage and tests the hot thickness d of battery after storage2, calculate cell thickness after 60 DEG C of constant temperature of battery store 7 days
Expansion rate；After battery at room temperature cooling for 24 hours, battery is subjected to constant-current discharge to 2.8V with 0.5C again, battery is recorded and deposits
Discharge capacity C after storage1, and calculate capacity surplus ratio after 60 DEG C of constant temperature of battery store 7 days, calculation formula are as follows: after 60 DEG C store 7 days
Cell thickness expansion rate=(d2-d1)/d1* 100%；Capacity surplus ratio=C after 60 DEG C of constant temperature store 7 days1/C0* 100%；
3) 45 DEG C of cycle performance tests of battery: at 45 DEG C, the battery after partial volume is charged to 4.2V by 1C constant current constant voltage, is cut
Only electric current 0.05C is recycled according to this then by 1C constant-current discharge to 2.8V, is calculated the 800th cycle after charge/discharge 800 times circulations and is followed
Ring capacity retention ratio, calculation formula are as follows: the 800th circulation volume conservation rate (%)=(the 800th cyclic discharge capacity/for the first time
Cyclic discharge capacity) × 100%.
The results are shown in Table 2 for the electric performance test of lithium-ion battery electrolytes in embodiment 1-14 and comparative example 1-9.
The electric performance test result of lithium-ion battery electrolytes in table 2 embodiment 1-14 and comparative example 1-9
Comparative example 1 is known to compared with embodiment 1-6 electric performance test result in table 2: novel film for additive in the present invention
The cycle performance and the capacity retention ratio after high temperature storage that battery can be obviously improved can speculate that silicon substrate class additive can
The protective film of one layer of uniform flexible is formed on silicon based anode material surface, this layer of protective film can effectively alleviate silicon carbon material
Expansion and contraction in charge and discharge process lead to the dusting and cracking of material.
Embodiment 1 is known to compared with 2 electric performance test result of embodiment in table 2: 1 good electrical property of embodiment in embodiment 2,
Reason is that unsaturated triple carbon-carbon bonds quality of forming film does not have unsaturated carbon-carbon double bond lotus good, greatly may be very acetylenic substance at
Membrane impedance is big.
Embodiment 11 and 13 electric performance test result of embodiment are relatively known in table 2: the electrical property of embodiment 13 is better than real
Example 11 is applied, the substance VEC containing unsaturated bond is added in embodiment 13, the substance is good in cathode film formation stability, has good
Toughness can adapt to the expansion and contraction of silica-base material, while VEC can be good at improving the high-temperature behavior of battery.
Embodiment 1, embodiment 7 and 8 electric performance test result of embodiment are relatively known in table 2: chemical combination in new additive agent
The additive amount of object 1 is more appropriate 1.0% or so.When additional amount is very few, new additive agent is poor in silicon-based anode quality of forming film,
Battery electrical property is caused not reach requirement.When additional amount is excessive, the additive of non-coating moiety has very battery storage performance
Big harm.
The electric performance test result of comparative example 2-5 is relatively known in table 2: fluorinated ethylene carbonate (FEC) can be apparent
Improve the cycle performance of silicon-based anode lithium ion battery, but with the increase of FEC content, battery high-temperature cycle performance and high temperature
Storage performance can be deteriorated.
In table 2 embodiment 1-8 and embodiment 9-14 electric performance test result relatively known to: be used alone that silicon substrate class is novel to be added
Add agent, the requirement of battery electrical property can't be fully achieved, it is also necessary to other types of additive be added, have between additive
Interaction, the common electrical property for improving battery.
Further, it compares and LiPF is used alone6As electric conducting lithium salt, embodiment 1-14 is added to good filming
Silicon-based anode lithium is effectively promoted in the novel conductive lithium salts difluorophosphate of characteristic, various new being applied in combination for lithium salts of film forming
Ion battery cycle performance and high-temperature storage performance.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of silicon-based anode non-aqueous electrolyte for lithium ion cell includes electrolyte lithium salt, non-aqueous organic solvent and film forming addition
Agent, which is characterized in that contain silicon base compound shown in formula (I) structure in the film for additive:
Wherein, R be selected from carbon atom number be 1~4 alkyl, alkenyl, alkynyl, H atom, F atom, contain fluoroalkyl and phenyl, institute
Stating on the base carbon of middle-end containing fluoroalkyl containing number of fluorine atoms is 0~3, containing number of fluorine atoms is 0~2 on other carbon atoms.
2. silicon-based anode non-aqueous electrolyte for lithium ion cell according to claim 1, which is characterized in that the film forming addition
Also contain conventional anode film for additive in agent, the conventional anode film for additive is selected from vinylene carbonate, fluoro carbonic acid
Vinyl acetate, vinylethylene carbonate, 1,3- propane sultone, 1,3- propylene sultones, ethylene sulfite, three (front threes
Base silane) one of phosphate, three (trimethyl silane) borates and methane-disulfonic acid methylene ester or a variety of；Preferably, institute
The quality for stating fluorinated ethylene carbonate accounts for the 5.0%~10.0% of the electrolyte gross mass, the vinylethylene carbonate or
The quality of 1,3- propylene sultones accounts for the 0.01%~1.2% of the electrolyte gross mass；It is further preferred that the film forming
Contain vinylene carbonate, 1,3- propane sultone, fluorinated ethylene carbonate and three (trimethyl silane) boric acid in additive
Ester, or containing vinylene carbonate, 1,3- propane sultone, fluorinated ethylene carbonate, three (trimethyl silane) borates and
Vinylethylene carbonate；It is furthermore preferred that containing vinylene carbonate, 1,3- propane sultone, fluorine in the film for additive
For ethylene carbonate and three (trimethyl silane) borates, and its additional amount be respectively electrolyte gross mass 1.0%, 1.0%,
10.0%, 1.5%；Or contain vinylene carbonate, 1,3- propane sultone, fluorinated ethylene carbonate, three (trimethyl silicanes
Alkane) borate and vinylethylene carbonate, and its additional amount be respectively electrolyte gross mass 1.0%, 1.0%, 10.0%,
1.5%, 0.5%.
3. silicon-based anode non-aqueous electrolyte for lithium ion cell according to claim 1, which is characterized in that described that there is formula
(I) silicon base compound shown in structure is selected from one of compound 1-6 or a variety of:
Preferably, the quality with silicon base compound shown in formula (I) structure accounts for the 0.01% of the electrolyte gross mass
~3.0%, such as 0.9%~1.1%, for another example 1%；It is highly preferred that account for the electrolyte total for the quality of the film for additive
The 0.5%~15.0% of quality.
4. silicon-based anode non-aqueous electrolyte for lithium ion cell according to claim 1, which is characterized in that the electrolyte lithium
Salt be one of lithium hexafluoro phosphate, double fluorine sulfimide lithiums, difluorophosphate and difluorine oxalic acid boracic acid lithium or more than one
Mix lithium salts, for example, the mixing lithium salts or lithium hexafluoro phosphate of lithium hexafluoro phosphate and difluorophosphate, double fluorine sulfimide lithiums and
The mixing lithium salts of the mixing lithium salts or lithium hexafluoro phosphate of difluorophosphate, difluorophosphate and difluorine oxalic acid boracic acid lithium；It is preferred that
Ground, the electrolyte lithium salt additive amount account for the 13.0%~17.5% of the electrolyte gross mass.
5. silicon-based anode non-aqueous electrolyte for lithium ion cell according to claim 4, which is characterized in that the electrolyte lithium
Salt is the mixing lithium salts of lithium hexafluoro phosphate and difluorophosphate, and additive amount accounts for the electrolyte gross mass respectively
15.0wt%, 1.0wt%；It or is lithium hexafluoro phosphate, the mixing lithium salts of double fluorine sulfimide lithiums and difluorophosphate, additive amount
15.0%, 2.0%, the 1.0% of the electrolyte gross mass is accounted for respectively；It or is lithium hexafluoro phosphate, difluorophosphate and difluoro grass
The mixing lithium salts of sour lithium borate, additive amount account for 15.0%, 1.0%, the 1.0% of the electrolyte gross mass respectively.
6. silicon-based anode non-aqueous electrolyte for lithium ion cell according to claim 1, which is characterized in that described non-aqueous organic
Solvent includes cyclic carbonate and linear carbonate, it is preferable that the cyclic carbonate is selected from ethylene carbonate and propylene carbonate
One of ester is a variety of, and the chain ester is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, two (2,2,2- trifluoros
Ethyl) one of carbonic ester and methyl trifluoro ethyl carbonate ester or a variety of；Preferably, the additive amount of the cyclic carbonate accounts for
The 20.0%~45.0% of the electrolyte gross mass, wherein the additive amount of propene carbonate accounts for the electrolyte gross mass
5.0%~20.0%；It is highly preferred that the non-aqueous organic solvent includes ethylene carbonate, diethyl carbonate and methyl ethyl carbonate,
And ethylene carbonate, diethyl carbonate and methyl ethyl carbonate 20:15:15:50 in mass ratio are mixed.
7. a kind of silicon-based anode lithium ion battery, which is characterized in that the silicon-based anode lithium ion battery includes cathode sheet, sun
Pole pole piece, the isolation film being placed between cathode sheet and anode pole piece and silicon-based anode lithium described in any one of claims 1-6
Ion battery nonaqueous electrolytic solution.
8. silicon-based anode lithium ion battery according to claim 7, which is characterized in that the cathode sheet includes aluminium foil collection
Fluid and cathode diaphragm, the anode pole piece include copper foil current collector and anode diaphragm；Preferably, the cathode diaphragm includes yin
Pole active material, conductive agent and binder, the anode diaphragm include anode active material, conductive agent and binder.
9. silicon-based anode lithium ion battery according to claim 8, which is characterized in that the cathode active material is
LiNi1-x-y-zCoxMnyAlzO2Or LiAmBnPO4, wherein 0≤x≤1,0≤y≤1,0≤z≤1,0≤m≤1,0≤n≤1 and 0
≤ x+y+z≤1, A, B represent Fe, Mn, Co or V.
10. silicon-based anode lithium ion battery according to claim 8, which is characterized in that the anode active material is to receive
Rice silicon, silicon alloy, SiOwThe Si-C composite material being combined with graphite, it is preferable that the SiOwTo aoxidize sub- silicon, silica
Or other silica-base materials.
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