CN107248567B - A kind of anode slice of lithium ion battery and lithium ion battery for mending lithium - Google Patents
A kind of anode slice of lithium ion battery and lithium ion battery for mending lithium Download PDFInfo
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- CN107248567B CN107248567B CN201710552846.XA CN201710552846A CN107248567B CN 107248567 B CN107248567 B CN 107248567B CN 201710552846 A CN201710552846 A CN 201710552846A CN 107248567 B CN107248567 B CN 107248567B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses one kind can mend the anode slice of lithium ion battery of lithium and lithium ion secondary battery containing such anode pole piece.Such anode pole piece can provide lithium source in initial charge, the consumption of lithium when to play compensation anode and cathode formation SEI film, promote first charge-discharge efficiency and cycle performance, discharge capacity and energy density can also be promoted, it is particularly suitable for the lower cathode system of first charge-discharge efficiency, such as: the cathode system containing silicon, silicon alloy, Si oxide or tin, tin alloy, tin-oxide.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, and in particular to one kind can mend the lithium ionic cell positive pole of lithium
Piece
With the lithium ion secondary battery for containing such anode pole piece.
Background technique
Lithium ion secondary battery has the advantages that high voltage, high-energy density, is widely used in consumer electronics product, storage
The power supply of energy system, dynamical system, the energy density for promoting lithium ion battery is that industrial circle and educational circles are concerned about the most all the time
The problem of.
During the initial charge of battery, positive and negative pole surface, which forms surface solid dielectric film (SEI film), can consume lithium,
By the irreversible carbonate for being cured as lithium of lithium or alkoxide, ester salt etc., to cause the loss of reversible lithium, reduction is imitated for the first time
Rate reduces discharge capacity of the cell.Especially using the new type of negative active material of some high capacity (silicon, silicon alloy, silicon oxidation
Object or tin, tin alloy, tin-oxide etc.) when, the capacitance loss of initial charge process shows particularly evident.
To promote first charge discharge efficiency, make up the lithium loss that initial charge forms SEI film, a kind of existing method of passage be
Lithium additive is mended in anode or cathode pole piece addition.Such as application publication number is the special of CN102916164A and CN102916165A
Sharp document proposes to be sprayed at positive and negative anodes pole piece respectively using the solution of organolithium as lithium additive is mended；In another example application is public
The patent document that cloth number is CN1290209C proposes that lithium metal, which is mixed together homogenate as benefit lithium additive and negative electrode material, to be applied
It covers；A kind of method that the patent document that such as application publication number is CN1830110A again proposes prelithiation, is equally by lithium metal
Positive or negative pole material is added, makes the compensation lithium ion loss of positive and negative pole material prelithiation.
It can be seen that the prior art has mainly used two kinds of benefit lithium additives, one is lithium metal, another kind is organic
Lithium.When using lithium metal, the aridity of environment is required high, powdered lithium metal reactivity is very high, inflammable, Workflow
It splashes, it is difficult to manufacture processing, in inside battery it is possible that residual lithium metal, brings potential danger in subsequent use；Using organic
When lithium solution, it is dangerous to can avoid powder bring, but often activity is higher for organolithium, or even generally requires during being made
Processing can not be manufactured in air using inert atmosphere protection, while also very sensitive to moisture, be difficult to prior art simultaneous
Hold.
In many existing researchs, the oxide M O of section transitions metal (such as Mn, Fe, Co, Ni, Cu, Cr)xBy conduct
The potential application of the negative electrode material of lithium ion battery.Its principle of electrochemical reaction and the embedding lithium of the interlayer of graphite/de- lithium are different, also with
The alloying of the metals such as silicon, tin, zinc/no-alloyed process is different, and reaction principle is as follows: lithium insertion reaction MOx+2xLi→M+
xLi2O+xe-To lithium current potential generally between 0~2V；Lithium abjection reaction (i.e. back reaction) M+xLi2O+xe-→MOx+ 2xLi pairs
Lithium current potential is generally between 1~3V.
Summary of the invention
The anode slice of lithium ion battery of lithium can be mended the purpose of the present invention is to provide one kind and contains such anode pole piece
Lithium ion secondary battery.
The present invention provides a kind of anode slice of lithium ion battery, contains benefit lithium additive, and conventional positive electrode active material
Matter, conductive agent, bonding agent, foil.The benefit lithium additive component is xLi2O·yM·zNmOnCompound.Wherein, y > 0, z > 0,
2x-y-z*m>0.1；M be Mn, Fe, Co, Ni, Cu, Cr element in it is one or more, N Mn, Fe, Co, Ni, Cu, Al, Mg, Ti,
Zn, Si, Cr's is one or more, including but not limited to Fe3O4、Co3O4、Mn2O3、NiO、Al2O3、SiO2、SnO2、TiO2、
CoaNibMncO (0.5 a+b+c≤1 <), Cu2O、ZnO、MgO、Cr2O3Deng.
Its principle may be: M+xLi has occurred in initial charge2O+xe-→MOxThe lithium of+2xLi deviates from reaction, thus
Play the role of mending lithium.Since the additive is in anode, in later charge and discharge process, current potential is it is not possible that as low as can
MO occursx+2xLi→M+xLi2O+xe-0~2V of reaction, so the benefit lithium additive only can not when charging first time
Inverse offer lithium, and lithium will not be consumed in subsequent charge and discharge process, to play the role of mending lithium source.
To ensure its validity, ingredient xLi2O·yM·zNmOnCompound in, M should be metal simple-substance, and valence state is answered
For 0 valence.
It is xLi in ingredient2O·yM·zNmOnCompound in, preferred NmOnIn metal N be not entirely in it most
That is, there are one or more N in high oxidation statemOn+pThe Common oxides of (p > 0).Work as NmOnIn metal N be not entirely in
When its highest oxidation state, lithium abjection reaction can write M+ (x+p) Li2O+NmOn+(x+p)e-→MOx+2(x+p)Li+
NmOn+2p, can so there are more lithiums to deviate from, additive amount can be less, more effectively as benefit lithium additive.
Since metal M plays the role of similar catalyst, metal M and Li in this reaction2O needs certain contact
It can just play a role, ratio exists preferably, and ingredient is preferably in xLi2O·yM·zNmOnIn 1.1 2x:y≤10 <.More
Preferably, this kind mends lithium additive xLi2O·yM·zNmOnMetal M be it is one or more in Mn, Co, Ni element, and N is
Mn, Co, Ni, Al, Mg, Ti, Sn's is one or more.In this way, after complete or not exclusively de- lithium, the ingredient of the benefit lithium additive
Can be consistent with positive active material ingredient, the subsequent positive active material that can be used as participates in charge and discharge, to further promote electricity
The capacity in pond.
Further, lithium additive xLi is mended2O·yM·zNmOnIn, it is one or more in M Mn, Co, Ni element.
Further, lithium additive xLi is mended2O·yM·zNmOnIn, NmOnFor Fe2O3、CoO、Mn2O3、NiO、Al2O3、
TiO2、CoaNibMncO、Cu2O、ZnO、Cr2O3、SiOd, SnO2, SnO, one of MgO or a variety of；CoaNibMnc0.5 < a in O
+ b+c≤1, SiOdMiddle d≤2.
More particularly, benefit lithium additive xLi2O·yM·zNmOnChemical component can be 2Li2O·
CoaNibMnc·(CodNieMnf) O (a+b+c=1,0.5 < d+e+f≤1), such as 2Li2OCoCoO, 2Li2O·Ni1/3Co1/ 3Mn1/3·(Ni1/3Co1/3Mn1/3) O etc..The advantages of ingredient, is that the portion of product after its de- lithium can be used as normal anode ginseng
In reacting with subsequent reversible removal lithium embedded, battery capacity is further increased.
Need to illustrate positive active material, conductive agent, bonding agent and foil of the anode pole piece in addition to mending lithium additive
Additional limitation is not done, it is applicable.
The ingredient that this kind mends lithium additive has been defined, but its addition manner can be and add as powder particle in homogenate
Add, be also possible to be previously deposited film in foil and be added, or redeposited film carries out after the completion of anode pole piece coating
Addition.
This kind mend lithium additive can be prepared by oneself, preparation method the following steps are included:
(1) compound of M, the compound of N and lithium metal are mixed according to chemical ratios；
(2) by the mixture sintering of step (1) under protective atmosphere state；
(3) product of step (2) and the gas containing X or solution or solid one or more steps are carried out to mix and anti-
It answers, obtains final product.
For guarantee lithium metal sufficiently reacted with the compound of the compound of M, N, in step (2), sintering temperature be 120~
250 DEG C, when lithium is in or when close to molten state, is reacted more rapid.
The reaction temperature of step (3) is -50~150 DEG C.
By step (2), lithium metal partly or entirely restores the compound of the compound of M, N, may generate for example
xLi2The compound of OyMzN, due to the metallic particles very little being reduced out, primary particle is in Nano grade, so active
Still very high, it can not be stabilized in humid air or solution in many cases.Therefore, it is necessary to one to be scheduled on controllable condition
Under, by step (3), the particle surface of the product of step (2) is passivated with gas, solution or solid, in particle table
Face generates oxide passivation layer, to make the stable benefit lithium additive, safety and be applicable to existing battery preparation technique process.
The present invention also provides a kind of lithium ion secondary battery, containing above-mentioned anode pole piece, cathode pole piece, be located at positive and negative anodes it
Between diaphragm, electrolyte, electrode leads to client and shell composition.
Preferably, the weight percent that lithium additive is mended in anode slice of lithium ion battery accounts for anode pole piece (except foil) weight
0~20wt% of amount is free of 0wt%.
Particularly, in the cathode pole piece of this lithium ion battery containing silicon, silicon alloy, Si oxide or tin, tin alloy,
When the negative electrode material of the lower first charge discharge efficiency such as tin-oxide, the effect for mending lithium and promotion first charge discharge efficiency is particularly evident.
Simultaneously as the consumption of its irreversible lithium supplemented with battery, also there is the circulation volume conservation rate for promoting battery
Beneficial effect.
Compared with the prior art, the advantages of the present invention are as follows: adding in anode using a kind of ingredient is xLi2O·yM·
zNmOnBenefit lithium additive, do not use lithium metal or organic lithium source, it is easily fabricated.The anode pole piece can be in battery initial charge
When discharge lithium, reversible lithium loss when supplementing initial charge is also promoted and is followed to have high first charge discharge efficiency and high-energy density
Ring capacity retention ratio is particularly suitable for the lower cathode system of first charge-discharge efficiency, such as: it is multiple containing silicon, silicon alloy, silicon-carbon
Close the cathode system of object, Si oxide or tin, tin alloy, tin-oxide.
Specific embodiment
In order to which technical problem, technical solution and beneficial effect solved by the invention is more clearly understood, tie below
Embodiment is closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention is not intended to limit the present invention.
Representative cells manufacturing instructions:
The preparation of anode pole piece:
(1) comparative example:
Positive electrode active materials cobalt acid lithium (LCO) or nickel manganese cobalt acid lithium (NCM), bonding agent Kynoar (PVDF) and conduction
Agent Super-P is added to stirring homogenate in N-Methyl pyrrolidone (NMP) according to the weight ratio in anode formula in following table and is made
Anode sizing agent；By anode sizing agent double spread on plus plate current-collecting body, after drying, compacting, cutting, cut-parts, soldering polar ear
Obtain anode pole piece.
(2) embodiment:
Positive electrode active materials cobalt acid lithium (LCO) or nickel manganese cobalt acid lithium (NCM), bonding agent Kynoar (PVDF), conduction
Agent Super-P and benefit lithium additive are added in N-Methyl pyrrolidone (NMP) according to the weight ratio in anode formula in following table
Anode sizing agent is made in stirring homogenate；By anode sizing agent double spread on plus plate current-collecting body, by drying, compacting, cutting, sanction
Anode pole piece is obtained after piece, soldering polar ear.
The preparation of cathode pole piece: negative electrode active material artificial graphite, butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC)
(or containing silicon, silicon alloy, silicon-carbon compound, Si oxide or tin, tin alloy, tin-oxide), weight as requested is such as
96:2:2 is added stirring homogenate in deionized water and negative electrode slurry is made；By negative electrode slurry double spread on negative current collector, warp
Cathode pole piece is obtained after crossing drying, compacting, cutting, cut-parts, soldering polar ear.
It should be understood that positive and negative anodes active material and ratio (as shown in table 1) have area in following comparative example and embodiment
Not, anode is added to and mends lithium additive in embodiment, and in addition to this, collector foil is identical, the unit area of anode pole piece
Coated weight it is identical, the coated length of positive and negative anodes pole piece is of same size, identical using electrolyte.
The preparation of electrolyte: select the lithium hexafluoro phosphate that concentration is 1M as lithium salts, with ethylene carbonate (EC): carbonic acid two
Ethyl ester (DEC): methyl ethyl carbonate (EMC), as solvent, additionally contains it assures that performance according to the weight ratio of 30:30:40
Conventional additives.
The preparation of lithium ion battery: the cathode pole piece and anode pole piece that are prepared according to previous process and diaphragm are carried out
Assembling, be made battery battery core, battery battery core is fitted into outer packing, to it inside inject electrolyte after seal, progress preliminary filling, and
It is melted into and lithium ion secondary battery is made.
Test method explanation:
Volume test: at 25 ± 2 DEG C, with the electric current constant-current charge of 1500mA to 4.35V, then in 4.35V constant-voltage charge
It is less than 60mA to electric current, obtains charging capacity, shelve 5 minutes, with 1500mA electric current constant-current discharge to 3.0V, obtains electric discharge and hold
Amount.
First charge discharge efficiency test: discharge capacity × 100% of first charge discharge efficiency=(priming volume+initial charge capacity)/for the first time
Loop test: with the electric current constant-current charge of 1500mA to 4.35V, then it is less than in 4.35V constant-voltage charge to electric current
60mA is shelved 5 minutes, with 1500mA electric current constant-current discharge to 3.0V, is recycled with this.300th capacity retention ratio=300th
Discharge capacity × 100% of secondary discharge capacity/for the first time.
Comparative example and embodiment explanation:
Illustrate: positive and negative anodes active material and ratio (as shown in table 1) are had any different, and anode is added to benefit lithium and adds in embodiment
Add agent, in addition to this, collector foil is identical, and the coated weight of the unit area of anode pole piece is identical, the coating of positive and negative anodes pole piece
Length x Width is identical, identical using electrolyte.Each embodiment and comparative example make 35 batteries, and data are average value in table.
LCO is LiCoO2, NCM LiNi1/3Co1/3Mn1/3O2。
SiCxFor silicon-carbon composite cathode material, SnMxFor tin alloy class negative electrode material.
It is as follows to mend lithium additive A, B, C, D, E, F, G, H, I, J, K, L chemical component:
A:4Li2O·Fe·0.5Al2O3
B:2.5Li2O·Fe·SnO2
C:3Li2O·Cu·Fe2O3
D:2.5Li2O·Ni·ZnO
E:2Li2O·Co·0.5Al2O3
F:2Li2O·Co·SnO2
G:3Li2O·Co0.5Fe0.5·TiO2
H:2Li2O·Co·SnO
I:3Li2O·Fe0.5Co0.5·CoO
J:2.5Li2O·Fe·SnO
K:2Li2O·Co·CoO
L:2Li2O·Ni1/3Co1/3Mn1/3·(Ni1/3Co1/3Mn1/3)O
The production reference battery production of the battery of the Comparative Examples 1 to 5 and embodiment 1~19 illustrates to make.
The positive piece preparation method of embodiment 20: particle, conductive carbon black, PVDF binder that ingredient is H are mixed,
In, the weight ratio that the weight ratio of conductive carbon black is 0~5%, PVDF is 1~10%, is added in N-Methyl pyrrolidone (NMP)
Additive slurry is made in stirring homogenate, and the film to form H is coated and dried on plus plate current-collecting body foil surface, then anode is starched
Material coating is deposited into the film for being divided into H on this coating with the method for chemical vapor deposition on plus plate current-collecting body foil surface,
Again by anode sizing agent coating on this coating.Other battery preparation step reference batteries make explanation.
The positive piece preparation method of embodiment 21: the step of illustrating with initial reference to battery production exists anode sizing agent dual coating
On plus plate current-collecting body, after drying, particle, conductive carbon black, PVDF binder that ingredient is H are mixed, wherein the weight of conductive carbon black
Amount be 1~10% than the weight ratio for be 0~5%, PVDF, is added in N-Methyl pyrrolidone (NMP) to stir to be homogenized to be made and adds
Add agent slurry, and is coated in positive electrode surface and dry the film to form H.Other battery preparation step reference batteries make explanation.
Analysis of experimental results:
Examples 1 to 21 is compared with the Comparative Examples 1 to 5, it can be seen that has used containing benefit lithium additive xLi2O·yM·
zNmOnAnode pole piece battery, all there is beneficial effect for promoting battery first charge discharge efficiency and cycle performance, particularly with containing
There is the lower cathode of the first charge discharge efficiencies such as silicon class and tin class, promotes effect and become apparent.Embodiment 17~21, it can be seen that no
Battery first charge discharge efficiency and cycle performance are only improved, the discharge capacity for the first time of battery is also improved.
According to above-mentioned principle, the present invention can also be made appropriate changes and modifications to the above embodiments.Therefore, this hair
The bright specific embodiment for being not limited to be explained above and describe should also be as some modifications and changes of the invention to fall into this
In the scope of protection of the claims of invention.In addition, although being used some specific terms in this specification, these terms
Merely for convenience of description, it does not limit the present invention in any way.
Claims (10)
1. a kind of anode slice of lithium ion battery, it is characterized in that: containing lithium additive is mended, which is xLi2O·
yM·zNmOnCompound；Wherein, y > 0, z > 0,2x-y-z*m > 0.1；M is a kind of or more in Mn, Fe, Co, Ni, Cu, Cr element
Kind, and M valence state is 0 valence；N is the one or more of Mn, Fe, Co, Ni, Cu, Al, Ti, Zn, Cr, Sn, Si, Mg.
2. anode pole piece according to claim 1, it is characterised in that: mend lithium additive xLi2O·yM·zNmOnIn, N is
Mn, Co, Ni, Al, Sn, Ti's is one or more.
3. anode pole piece according to claim 1, it is characterised in that: mend lithium additive xLi2O·yM·zNmOnIn, NmOn
In metal N average valence be less than its highest oxidation valence state.
4. anode pole piece according to claim 1, it is characterised in that: mend lithium additive xLi2O·yM·zNmOnIn, 1.1
2x:y≤10 <.
5. anode pole piece according to claim 1, it is characterised in that: mend lithium additive xLi2O·yM·zNmOnIn, M is
It is one or more in Mn, Co, Ni element.
6. anode pole piece according to claim 1, it is characterised in that: mend lithium additive xLi2O·yM·zNmOnIn, NmOn
For Fe2O3、CoO、Mn2O3、NiO、CoaNibMncO、Cu2O、Cr2O3、SiOd, one of SnO or a variety of；CoaNibMnc0.5 in O
< a+b+c≤1, SiOdMiddle d < 2.
7. anode pole piece according to claim 1, it is characterised in that: benefit lithium additive is 2Li2O·CoaNibMnc·
(CodNieMnf) O, wherein a+b+c=1,0.5 < d+e+f≤1.
8. anode pole piece described according to claim 1~any one of 7, it is characterised in that: mend the weight hundred of lithium additive
Divide 0~20wt% than the anode pole piece weight after accounting for except foil, is free of 0wt%.
9. a kind of lithium ion secondary battery, it is characterized in that: contain positive pole described according to claim 1~any one of 8
Piece, the diaphragm between positive and negative anodes, cathode pole piece, electrolyte, electrode leads to client and shell.
10. lithium ion secondary battery according to claim 9, it is characterized in that: in its cathode pole piece containing silicon, silicon alloy,
One of silicon-carbon compound, Si oxide, tin, tin alloy, tin-oxide are a variety of.
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| KR20190062209A (en) * | 2017-11-27 | 2019-06-05 | 주식회사 엘지화학 | Additives for cathode, manufacturing method of the same, cathode including the same, lithium recharegable battery including the same |
| CN108511758B (en) * | 2018-03-23 | 2020-08-18 | 安普瑞斯（无锡）有限公司 | Negative electrode aqueous lithium supplement additive and preparation method thereof |
| CN109004195B (en) * | 2018-07-24 | 2021-01-15 | 安普瑞斯（无锡）有限公司 | Lithium supplement additive and preparation method thereof |
| CN110247106B (en) * | 2019-05-25 | 2021-11-19 | 浙江锋锂新能源科技有限公司 | Mixed solid-liquid electrolyte battery with titanium niobate |
| CN110176641A (en) * | 2019-06-03 | 2019-08-27 | 哈尔滨工业大学 | A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry |
| CN111525096B (en) * | 2020-03-30 | 2021-10-22 | 维达力实业(深圳)有限公司 | Negative plate, preparation method thereof and battery |
| CN111640932B (en) * | 2020-06-03 | 2022-05-13 | 无锡零一未来新材料技术研究院有限公司 | High-purity positive electrode lithium supplement additive, preparation method thereof and lithium ion battery |
| CN111799457B (en) * | 2020-07-30 | 2022-10-18 | 广东邦普循环科技有限公司 | Pre-lithiation-treated lithium ion positive electrode material and preparation method and application thereof |
| CN112701277A (en) * | 2020-12-24 | 2021-04-23 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery prelithiation additive and application thereof |
| CN114790131A (en) * | 2021-01-25 | 2022-07-26 | 孚能科技(赣州)股份有限公司 | Positive electrode lithium supplement additive, positive electrode plate, preparation method of positive electrode plate and lithium ion battery |
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| CN102916165B (en) * | 2012-09-20 | 2016-05-18 | 东莞新能源科技有限公司 | A kind of method of mending lithium to anode plate for lithium ionic cell |
| CN105098188B (en) * | 2014-04-28 | 2017-09-01 | 比亚迪股份有限公司 | A kind of anode material for lithium-ion batteries additive and preparation method thereof, positive electrode and lithium ion battery containing the additive |
| CN103996820A (en) * | 2014-05-30 | 2014-08-20 | 南京安普瑞斯有限公司 | Lithium ion battery as well as mixed positive electrode and active material with synergistic effect |
| CN106898737A (en) * | 2015-12-21 | 2017-06-27 | 比亚迪股份有限公司 | A kind of anode material for lithium-ion batteries additive and preparation method thereof, positive electrode and lithium ion battery containing the additive |
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