CN108281709A - A kind of low temperature resistant extra long life lithium titanate battery and preparation method thereof - Google Patents
A kind of low temperature resistant extra long life lithium titanate battery and preparation method thereof Download PDFInfo
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- CN108281709A CN108281709A CN201810019897.0A CN201810019897A CN108281709A CN 108281709 A CN108281709 A CN 108281709A CN 201810019897 A CN201810019897 A CN 201810019897A CN 108281709 A CN108281709 A CN 108281709A
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- 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
- H01M10/058—Construction or manufacture
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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
- H01M10/056—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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of low temperature resistant extra long life lithium titanate batteries and preparation method thereof.The positive electrode active material that the lithium titanate battery uses is a kind of powder with low grain size and particle size dispersion narrow range, slurry granularity obtained is low after powder stirring, pole piece surface density coherence request obtained is high after coating, low temperature additive is added in the electrolyte used, diaphragm is nonwoven cloth diaphragm.Compared with prior art, the lithium titanate battery that the present invention announces has the cycle life of excellent low temperature charge-discharge performance and overlength, the lithium titanate battery can be used on low temperature and the electric vehicle of severe cold area, and requiring relatively high field also in military project, aerospace etc. has wide application space.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of extra long life titaniums with good low temperature properties
Acid lithium battery.
Background technology
Lithium ion battery has high operating voltage, high ratio energy relative to lead-acid accumulator, nickel-cadmium cell, Ni-MH battery
The advantages that amount, therefore have been widely used.But the research of current lithium ion battery low-temperature characteristics relatively lags behind, and cannot be satisfied
People require lithium ion battery in the charge-discharge performance in northern frore area or field, when use environment temperature is less than 0 DEG C,
Battery performance, which substantially declines, to be dropped or can not work normally, and at low ambient temperatures, heating plate heating need to be equipped with to battery and ensures that it is normal
Charge/discharge operation.
Lithium titanate is a kind of zero strain material, hardly happens any variation with volume when completely putting completely filling, can avoid
Capacity attenuation caused by volume change in cyclic process, thus using lithium titanate as the lithium ion battery of anode active material ratio with
Graphite, tin silicon alloy have longer cycle life as the lithium ion battery of anode active material.Meanwhile using lithium titanate as
The lithium ion battery of anode active material has preferably peace relative to the lithium ion battery using graphite as anode active material
Full performance and cryogenic property.In addition, lithium titanate is about 1.55V relative to the current potential of lithium, much larger than analysis lithium current potential, therefore will not go out
Phenomenon graphite like that due to analysing lithium caused by safety problem.As it can be seen that lithium titanate battery have long circulation life, low temperature, big multiplying power,
The advantages that high safety, still has potential application under the particular/special requirements such as severe cold.Therefore, low temperature resistant extra long life titanium is developed
Acid lithium battery is of great significance.
CN104409767A discloses a kind of low temp lithium ion secondary cell, which is that point is brilliant
Stone-type LiMn2O4, cathode electroactive material are spinel lithium titanate, ＜ -40 DEG C of the fusing point of electrolyte, viscosity ＜ 3cP, in low temperature
Under the conditions of can be had excellent performance with charge and discharge cycle under safe charging and low temperature.Research is pointed out, under low temperature, organic electrolysis fluid viscosity
Become larger, the migration of lithium ion is difficult, and polarization increases, if being filled at low temperature to the lithium ion battery of the graphite cathode system of lithium ion
Electricity easily causes lithium ion to be deposited on graphite cathode, forms Li dendrite, and penetrating diaphragm makes battery short circuit cause burning or quick-fried
It is fried, the safety problem of lithium ion battery failure is eventually led to, and cycle life is short.CN107195968A discloses a kind of lithium titanate
Battery, by adding poly(silicon aether) and difluorophosphate in electrolyte, it is suppressed that the decomposition of LiPF6 reduces HF contents, improves
Electrolyte and lithium titanate interface stability, effectively improve lithium titanate flatulence problem, improve the height of metatitanic acid lithium dynamical battery
Warm cycle performance and storge quality, low temperature output performance.As it can be seen that promoting the method for the low temperature performance of lithium ion battery very
It is more, but it is rarely seen to have extended cycle life, it is difficult to and the military project etc. in low temperature and severe cold area requires relatively high field extensive use.
Invention content
The technical problem to be solved by the present invention is to:A kind of low temperature resistant extra long life lithium titanate battery and its preparation side are provided
Method overcomes the problems, such as that charge-discharge performance is poor under existing lithium ion battery low temperature, cycle life is short.
The anode of low grain size can guarantee Li+There is larger diffusion coefficient in active material, with electrolyte contacts area
Greatly.Meanwhile positive grain size is smaller, Li+Move to that the path in electrolyte is shorter, and ionic conductivity is higher by crystal structure.This
Outside, pulp particle degree made from low grain size and the anode of particle size dispersion narrow range is small and microscopic uniformity is good, can improve coating
When the consistency of the surface density and uniformity of hole, stirring is coated with the cycle life that microcosmic consistent performance extends battery.Contain
Low temperature resistant electrolyte so that there is higher ionic conductivity at low temperature, effectively reduce battery charge and shift internal resistance, nonwoven
Cloth diaphragm can improve the wellability of electrolyte, and above several respects can improve the cryogenic property of ion battery, can also extend metatitanic acid
Lithium battery cycle life.Therefore, using low grain size and the positive electrode of particle size dispersion narrow range, work is coated with by distinctive stirring
Positive and negative anodes pole piece is made in skill, and uses nonwoven cloth diaphragm and the electrolyte of addition low temperature additive.
A kind of specifically low temperature resistant extra long life lithium titanate battery of present invention offer and preparation method thereof, feature exists
In：The positive electrode active material of the lithium titanate battery used is a kind of powder with low grain size and particle size dispersion narrow range,
Slurry granularity obtained is low after powder stirring, and pole piece surface density coherence request obtained is high after slurry coating, the electricity used
It solves and adds low temperature additive in liquid.
Further, it is characterised in that：Positive electrode active material is ternary material, the weight percentage ranges of anode sizing agent：Just
Pole 85%-98%, positive conductive agent 7%-1%, positive electrode binder 8%-1%；Negative electrode active material is lithium titanate, negative electrode slurry
Weight percentage ranges：Cathode 87%-98%, cathode conductive agent 1%-6%, negative electrode binder 1%-5%；Contain in electrolyte
Low temperature resistant additive.
Further, it is characterised in that：The positive electrode active material is ternary material LiNixCoyMnzO2, wherein x+y+z
=1,0≤x, y, z≤0,2 μm≤D50≤8 μm of median particle diameter, particle size dispersion narrow range.
Further, it is characterised in that：Positive conductive agent is one kind in carbon black, acetylene black, Super-P, KS-6, VGCF
Or two kinds of mixture, positive electrode binder PVDF.
Further, it is characterised in that：Negative electrode active material is lithium titanate, and cathode conductive agent is carbon black, acetylene black, Super-
P, the mixture of one or both of KS-6, VGCF, negative electrode binder PVDF.
Further, it is characterised in that：The diaphragm is nonwoven cloth diaphragm, and thickness is 14-30 μm, porosity 45-
72%, air penetrability 10-50cm3/sec.One side non-woven fabrics is ventilative and pulls out water, and the infiltration of electrolyte can be improved by not absorbing water
Property；Another aspect non-woven fabrics has antibiotic property, can prevent the erosion in the electrolytic solution such as bacterium, ensure long-term charge and discharge cycles
In battery quality.
Further, it is characterised in that：Low temperature resistant additive is added in the electrolyte, by electrolyte and solvent group
At wherein electrolyte is one or more of lithium hexafluoro phosphate, lithium perchlorate, trifluoromethyl sulfonic acid lithium；Solvent is EC (carbonic acid
Vinyl acetate), DMC (dimethyl carbonate), DEC (diethyl carbonate), EMC (methyl ethyl carbonate), PC (propene carbonate) and VC (carbon
Sour vinylene) in three kinds or a variety of, but at least contain PC and VC.In order to improve low temperature capacitance, added in solvent
PC components, the main polarization for reducing electrolyte under low temperature, increase charge migration speed.In order to further increase cycle performance, change
It is apt to the stability of SEI films, is added on a small quantity into the lower VC of film potential in electrolyte system.In negative terminal surface radical polymerization occurs for VC
Reaction is closed, poly- alkylcarbonic acid lithium compound is generated, to effectively inhibit the anti-inserted altogether of solvent molecule to answer, while anode is made without pair
With.Meanwhile two kinds of solvent collaborations can inhibit electrolyte decomposition, reduce HF contents, improve flatulence problem, and then promote the low of battery
Warm nature energy and cycle performance.
The present invention also provides a kind of method preparing above-mentioned low temperature resistant extra long life lithium titanate battery, feature exists
In：Due to the self-characteristic of low grain size positive electrode active material, dispersion effect is poor in a solvent, and there are slurry uniformity, stability
Difference easily drops off, electrode material is de- during poor performance at low temperatures and charge and discharge cycles coated on that there are surface densities on base material is uneven
The problems such as falling.When the present invention stirs, using the agitating mode of high speed dispersion so that slurry reaches microcosmic and macroscopical mixing, with
High dispersing uniformity is obtained, the stability of slurry is improved.
Further, it is characterised in that：It is first that positive electrode active material, conductive agent, binder is dry-mixed according to the ratio, it is then added molten
Agent NMP is 68%-70% to solid content, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；It is eventually adding solvent NMP
To the solid content for being easy to application viscosity, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm are stirred
Mix 80min；Overall process temperature controls between 17-25 DEG C, and a kind of low granularity anode sizing agent of non-newtonian fluid, viscosity is made
5000 ± 1000cps, size range D50≤15 μm are well positioned to meet the needs of follow-up coating process.Slurry is coated with,
It rolls, cut, be dried to obtain anode pole piece.
Further, it is characterised in that：Select lithium titanate as negative material.First by lithium titanate LTO, conductive agent SPC, viscous
Negative electrode slurry is made in dry powder blend, then addition solvent NMP stirrings to knot agent PVDF according to the ratio, slurry is coated with, rolling, is cut,
It is dried to obtain cathode pole piece.
The present invention also provides a kind of method preparing above-mentioned low temperature resistant extra long life lithium titanate battery, feature exists
In：When the present invention is coated with, high-precision coating machine is used to improve the consistent of dressing amount on battery pole piece transverse direction and longitudinal direction direction
Property and smear bilateral symmetry, surface density error be ± 2.5 ‰, ensure the consistency between single pole piece.It also can guarantee so small
Small and uniform hole is formed between grain size active material particle, conductive carbon particle and binder, thus it is viscous to be conducive to enhancing
Effect is tied, intergranular bonding force is also enhanced after roll-in, and the pole piece porosity after bonding is uniform and is not easy to lose powder.Ensure production
Product stable structure, stable chemical performance, platform stable, and then greatly improve the cryogenic property and service life of lithium ion battery.
The present invention also provides a kind of method preparing above-mentioned low temperature resistant extra long life lithium titanate battery, feature exists
In：The positive electrode, the negative electrode and the separator is made up of lamination or winding process.
Battery of the present invention has high low temperature and cycle performance, is suitable for the field high to battery request, such as low temperature ring
Energy-storage battery under border and electric vehicle battery, have broad application prospects.This battery requires -43 DEG C of low temperature in military products
Environment discharge capacity reaches the 59% of room temperature capacity, and after room temperature charge and discharge cycles 25000 times capacity maintenance rate 80% with
On.This breaches restriction of the low temperature to lithium ion battery applications range significantly, not only " can go on an expedition " low temperature with assisted electric vehicle
And severe cold area, and the field vehicle in military industry field, tank, field operation transport vehicle, the energy storage in frontier defense area and submarine, deep-sea
Detector, aircraft etc., which require relatively high field also, wide application space.
Description of the drawings
Fig. 1 is the cyclic curve under the conditions of 5C/1C
Fig. 2 is battery discharge curve under different temperatures
Specific implementation mode
In order to keep technical scheme of the present invention and advantage clearer, table and specific embodiment are to this hair below in conjunction with the accompanying drawings
It is bright to be described in detail.
The low temperature resistant extra long life lithium titanate battery of the present invention, the positive electrode active material used be it is a kind of have low grain size and
The powder of particle size dispersion narrow range, slurry granularity obtained is low after powder stirring, pole piece surface density one obtained after slurry coating
The requirement of cause property is high, and low temperature additive is added in the electrolyte used, and diaphragm is nonwoven cloth diaphragm.
The anode of low grain size can guarantee Li+There is larger diffusion coefficient in active material, with electrolyte contacts area
Greatly.Meanwhile positive grain size is smaller, Li+Move to that the path in electrolyte is shorter, and ionic conductivity is higher by crystal structure.This
Outside, pulp particle degree made from low grain size and the anode of particle size dispersion narrow range is small and microscopic uniformity is good, can improve coating
When the consistency of the surface density and uniformity of hole, stirring is coated with the cycle life that microcosmic consistent performance extends battery.Contain
Low temperature resistant electrolyte so that there is higher ionic conductivity at low temperature, effectively reduce battery charge and shift internal resistance, nonwoven
Cloth diaphragm can improve the wellability of electrolyte, and above several respects can improve the cryogenic property of ion battery, can also extend metatitanic acid
Lithium battery cycle life.Therefore, using low grain size and the positive electrode of particle size dispersion narrow range, work is coated with by distinctive stirring
Positive and negative anodes pole piece is made in skill, and uses nonwoven cloth diaphragm and the electrolyte of addition low temperature additive.
Wherein, positive electrode active material is ternary material, the weight percentage ranges of anode sizing agent：Positive 85%-98%, anode
Conductive agent 7%-1%, positive electrode binder 8%-1%；Negative electrode active material is lithium titanate, the weight percentage ranges of negative electrode slurry：
Cathode 87%-98%, cathode conductive agent 1%-6%, negative electrode binder 1%-5%；Contain low temperature resistant additive in electrolyte.
Positive electrode active material is ternary material LiNixCoyMnzO2, wherein x+y+z=1,0≤x, y, z≤0,2 μm of median particle diameter
≤ D50≤8 μm, particle size dispersion narrow range.Positive conductive agent be carbon black, acetylene black, one kind in Super-P, KS-6, VGCF or
Two kinds of mixture, positive electrode binder PVDF.
Negative electrode active material is lithium titanate, and cathode conductive agent is one kind in carbon black, acetylene black, Super-P, KS-6, VGCF
Or two kinds of mixture, negative electrode binder PVDF.
Diaphragm is nonwoven cloth diaphragm, and thickness is 14-30 μm, porosity 45-72%, air penetrability 10-50cm3/sec。
Non-woven fabrics is on the one hand ventilative and pulls out water, and the wellability of electrolyte can be improved by not absorbing water；Another aspect non-woven fabrics has antibiotic property,
The erosion in the electrolytic solution such as bacterium can be prevented, ensures the battery quality in long-term charge and discharge cycles, and above-mentioned parameter model
The non-woven fabrics enclosed so that ion passes through more unobstructed and have good electrical isolation.
Low temperature resistant additive is added in electrolyte, is made of electrolyte and solvent, and wherein electrolyte is lithium hexafluoro phosphate, height
One or more of lithium chlorate, trifluoromethyl sulfonic acid lithium；Solvent is EC (ethylene carbonate), DMC (dimethyl carbonate), DEC
(diethyl carbonate), three kinds or a variety of in EMC (methyl ethyl carbonate), PC (propene carbonate) and VC (vinylene carbonate),
But at least contain PC and VC.PC components are added in solvent, the main polarization for reducing electrolyte under low temperature increases charge migration speed
Degree, can improve low temperature capacitance.It is added in electrolyte system on a small quantity at the lower VC of film potential, VC is in negative terminal surface
Raolical polymerizable occurs, generates poly- alkylcarbonic acid lithium compound, to effectively inhibit the anti-inserted altogether of solvent molecule to answer, simultaneously
It is without side-effects to anode, cycle performance is can further improve, the stability of SEI films is improved.Meanwhile two kinds of solvent collaborations can inhibit
Electrolyte decomposes, and reduces HF contents, improves flatulence problem, and then promote the cryogenic property and cycle performance of battery.
Low temperature resistant extra long life lithium titanate battery of the present invention in the preparation, due to low grain size positive electrode active material
Self-characteristic, dispersion effect is poor in a solvent, there are slurry uniformity, stability are poor, coated on there are surface densities on base material
It is uneven, it easily drops off, the problems such as electrode material falls off during poor performance at low temperatures and charge and discharge cycles.When the present invention stirs, lead to
It crosses and uses planetary stirring machine, using the agitating mode of high speed dispersion so that slurry reaches microcosmic and macroscopical mixing, to obtain
High dispersing uniformity improves the stability of slurry.
Further, first that positive electrode active material, conductive agent, binder is dry-mixed according to the ratio in stirring, solvent is then added
NMP is 68%-70% to solid content, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；It is eventually adding solvent NMP extremely
It is easy to the solid content of application viscosity, pressure is less than under -90KPa vacuum conditions, revolution 25rmp, high speed dispersion 1500rpm, stirring
80min；Overall process temperature controls between 17-25 DEG C, and a kind of low granularity anode sizing agent of non-newtonian fluid, viscosity 5000 is made
± 1000cps, size range D50≤15 μm are well positioned to meet the needs of follow-up coating process.Slurry is coated with, is rolled,
It cuts, be dried to obtain anode pole piece.
Further, in the preparation as the lithium titanate of negative material, first by lithium titanate LTO, conductive agent SPC, binder
Negative electrode slurry is made in dry powder blend, then addition solvent NMP stirrings to PVDF according to the ratio, by slurry coating, rolling, cuts, dry
Obtain cathode pole piece.
Preferably, the present invention uses high-precision coating machine to improve battery pole piece transverse direction and longitudinal direction direction in coating
The consistency and smear bilateral symmetry of upper dressing amount, surface density error are ± 2.5 ‰, ensure the consistency between single pole piece.
It also can guarantee in this way and form small and uniform hole between small-particle diameter active material granule, conductive carbon particle and binder, because
And be conducive to enhance bond effect, intergranular bonding force is also enhanced after roll-in, bond after pole piece porosity uniformly and
It is not easy to lose powder.Ensure that product structure is stablized, stable chemical performance, platform stable, and then greatly improve the low temperature of lithium ion battery
Performance and used life.
With reference to specific embodiment, illustrate the solution of the present invention.
Embodiment 1：It is 3 μm of LiNi to select D501/3Co1/3Mn1/3O2(hereinafter referred to as NCM111) is used as positive electrode.First
(hereinafter referred to as by positive electrode active material NCM111, conductive agent acetylene black (hereinafter referred to as HS-100), binder polyvinylidene fluoride
PVDF), according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and it is (following that solvent N-methyl pyrilidone is then added
Abbreviation NMP) to solid content be 69%, revolution 15rmp, high speed dispersion 1200rpm, stir 120min；It is eventually adding solvent NMP extremely
Solid content is 65%, and pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Entirely
Process temperature controls between 17-25 DEG C, and anode sizing agent viscosity 5500cps, D50=13 μm of size range, by the slurry is made
Expect that coated face density error is ± 2.2 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.By lithium titanate LTO, conductive agent carbon black (hereinafter referred to as SPC), binder PVDF
Mixing is then added solvent NMP stirrings and negative electrode slurry is made.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.It will
Slurry is coated with, rolls, cuts, is dried to obtain cathode pole piece.
It is 15 μm to select thickness, porosity 52%, air penetrability 30cm3/ sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, nonwoven cloth diaphragm lamination.The electrolyte containing low temperature resistant additive, electrolyte are injected in battery
Lithium salts is lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/EMC/VC=3/2/4/1 (v/v/v/v).It, need to be to electricity after preliminary filling
Pond is exhausted.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 74% of temperature, under the conditions of -43 DEG C
Discharge capacity sustainment rate 59%；Discharge capacity sustainment rate 84% after 25000 cycles.
Embodiment 2：Select the NCM111 that D50 is 3 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=88:6:6 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 69%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
64%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5000cps, D50=12 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 2.3 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 15 μm to select thickness, and porosity 52%, air penetrability is that 30cm3/sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/EMC/VC=3/2/4/1 (v/v/v/v).After preliminary filling, battery need to be carried out
Exhaust.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 75% of temperature, discharges and holds under the conditions of -43 DEG C
Measure sustainment rate 61%；Discharge capacity sustainment rate 83% after 25000 cycles.
Embodiment 3：Select the NCM111 that D50 is 6 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 68.5%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
65%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5000cps, D50=14 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 2.3 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 20 μm to select thickness, porosity 45%, air penetrability 40cm3/ sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/DEC/VC=3/2/4/1 (v/v/v/v).After preliminary filling, battery need to be carried out
Exhaust.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 77% of temperature, discharges and holds under the conditions of -43 DEG C
Measure sustainment rate 62%；Discharge capacity sustainment rate 81% after 25000 cycles.
Embodiment 4：It is 6 μm of LiNi to select D500.5Co0.2Mn0.3O3(hereinafter referred to as NCM523) is used as positive electrode.First
By positive electrode active material NCM523, conductive agent HS-100, binder PVDF, according to NCM523：HS-100：PVDF=93:4:3 proportionings
Dry-mixed, it is 68.5% that solvent NMP, which is then added, to solid content, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Most
It is 64% that solvent NMP is added afterwards to solid content, and pressure is less than under -90KPa vacuum conditions, revolution 25rmp, high speed dispersion
1500rpm stirs 80min；Overall process temperature controls between 17-25 DEG C, and anode sizing agent viscosity 4800cps, granularity is made
The slurry coated face density error is ± 2.2 ‰ by D50=13 μm of range.It further rolls, cut, being dried to obtain positive pole
Piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 20 μm to select thickness, porosity 45%, air penetrability 40cm3/ sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/EMC/VC=3/1.5/4/1.5 (v/v/v/v).It, need to be to battery after preliminary filling
It is exhausted.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 73% of temperature, -43 DEG C of condition decentralizations
Capacitance sustainment rate 57%；Discharge capacity sustainment rate 80% after 25000 cycles.
Comparative example 1：Select the NCM111 that D50 is 12 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 68.5%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
65%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5000cps, D50=40 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 2.7 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 15 μm to select thickness, porosity 52%, air penetrability 30cm3/ sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/EMC/VC=3/2/4/1 (v/v/v/v).After preliminary filling, battery need to be carried out
Exhaust.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 50% of temperature, discharges and holds under the conditions of -43 DEG C
Measure sustainment rate 23%；Discharge capacity sustainment rate 81% after 2000 cycles.
Comparative example 2：Select the NCM111 that D50 is 3 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 69%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
64%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5500cps, D50=13 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 2.2 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 15 μm to select thickness, and porosity 52%, air penetrability is that 30cm3/sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/DEC/EMC/VC=3/3/4 (v/v/v).After preliminary filling, battery need to be arranged
Gas.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 36% of temperature, -43 DEG C of condition discharge capacities
Sustainment rate 10%；Discharge capacity sustainment rate 81% after 5000 cycles.
Comparative example 3：Select the NCM111 that D50 is 15 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 68.5%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
65%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5000cps, D50=45 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 3.0 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.Lithium titanate LTO, conductive agent SPC, binder PVDF are mixed, are then added
Negative electrode slurry is made in solvent NMP stirrings.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.Slurry is coated with, is rolled,
It cuts, be dried to obtain cathode pole piece.
It is 20 μm to select thickness, and porosity 45%, air penetrability is that 40cm3/sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, diaphragm lamination.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is
Lithium hexafluoro phosphate LiPF6, organic solvent is EC/DEC/EMC=3/3/4 (v/v/v).After preliminary filling, battery need to be exhausted.System
The battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 30% of temperature, and -43 DEG C of condition discharge capacities maintain
Rate 8%；Discharge capacity sustainment rate 81% after 1000 cycles.
Comparative example 4：Select the NCM111 that D50 is 3 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 69%, and revolve round the sun 20rmp, stirs 120min；It is 65% that solvent NMP, which is eventually adding, to solid content, and pressure is less than -90KPa
Under vacuum condition, revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature controls between 17-25 DEG C, system
Anode sizing agent viscosity 5500cps is obtained, which is ± 2.8 ‰ by D50=30 μm of size range.Into
One step rolls, cuts, is dried to obtain anode pole piece.
Select lithium titanate as negative material.By lithium titanate LTO, conductive agent carbon black (hereinafter referred to as SPC), binder PVDF
Mixing is then added solvent NMP stirrings and negative electrode slurry is made.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.It will
Slurry is coated with, rolls, cuts, is dried to obtain cathode pole piece.
It is 15 μm to select thickness, porosity 52%, air penetrability 30cm3/ sec diaphragms are nonwoven cloth diaphragm.It will be positive
Core is made in pole piece, cathode pole piece, nonwoven cloth diaphragm lamination.The electrolyte containing low temperature resistant additive, electrolyte are injected in battery
Lithium salts is lithium hexafluoro phosphate LiPF6, organic solvent is EC/PC/EMC/VC=3/2/4/1 (v/v/v/v).It, need to be to electricity after preliminary filling
Pond is exhausted.Battery obtained is under 1C discharging conditions, -20 DEG C of discharge capacity sustainment rates 47% of temperature, under the conditions of -43 DEG C
Discharge capacity sustainment rate 16%；Discharge capacity sustainment rate 81% after 5000 cycles.
Comparative example 5：Select the NCM111 that D50 is 3 μm as positive electrode.First by positive electrode active material NCM111, conductive agent
HS-100, binder PVDF, according to NCM111：HS-100：PVDF=93:4:3 proportionings are dry-mixed, and solvent NMP is then added to admittedly
Content is 69%, and revolution 15rmp, high speed dispersion 1200rpm stir 120min；Solvent NMP, which is eventually adding, to solid content is
64%, pressure is less than under -90KPa vacuum conditions, and revolution 25rmp, high speed dispersion 1500rpm stir 80min；Overall process temperature
Anode sizing agent viscosity 5500cps, D50=13 μm of size range, by the slurry coated face is made between 17-25 DEG C in control
Density error is ± 2.2 ‰.It further rolls, cut, be dried to obtain anode pole piece.
Select lithium titanate as negative material.By lithium titanate LTO, conductive agent carbon black (hereinafter referred to as SPC), binder PVDF
Mixing is then added solvent NMP stirrings and negative electrode slurry is made.Each ingredient distribution ratio is according to LTO：SPC：PVDF=94:3：3.It will
Slurry is coated with, rolls, cuts, is dried to obtain cathode pole piece.
Select common polyethylene porous separator.Volume is made in anode pole piece, cathode pole piece, polyethylene porous separator lamination
Core.The electrolyte containing low temperature resistant additive is injected in battery, electrolyte lithium salts is lithium hexafluoro phosphate LiPF6, organic solvent EC/
PC/EMC/VC=3/2/4/1 (v/v/v/v).After preliminary filling, battery need to be exhausted.Battery obtained under 1C discharging conditions,
- 20 DEG C of discharge capacity sustainment rates 45% of temperature, -43 DEG C of condition discharge capacity sustainment rates 18%；It discharges after 5000 cycles
Capacity maintenance rate 81%.
It is low temperature discharge, cycle performance and the flatulence of the lithium titanate battery of above-mentioned 4 embodiments and 5 comparative examples below
Situation test result：
Comparative example 1 is analyzed with embodiment it is found that ionic conductivity is low under cryogenic conditions, using 2 μm≤D50 of median particle diameter≤
8 μm of positive electrode, grain size is small, uniform particle sizes, and large specific surface area can guarantee Li+There is larger diffusion in active material
Coefficient is big with electrolyte contacts area so as to have high ionic conductivity and imbibition ability at low temperature.
Analysis comparative example 2 is with embodiment it is found that electrolyte point can be effectively inhibited by being added to PC and VC in electrolyte solvent
Solution reduces HF contents, improves the stability of lithium titanate and electrolyte interface, improves lithium titanate flatulence problem, promotes lithium titanate electricity
The low temperature discharge ability and cycle life in pond.
Analyze comparative example 4 and embodiment it is found that using low grain size and the positive electrode of particle size dispersion narrow range, process it is peculiar
Stirring coating process positive and negative anodes pole pieces is made, ensure the consistency between single pole piece, and then small-particle diameter active material granule, lead
Small and uniform hole is formed between carbon particles and binder, thus is conducive to enhance bond effect, after roll-in between particle
Bonding force be also enhanced, bond after pole piece porosity uniformly and be not easy to lose powder, greatly improve the low temperature of lithium ion battery
Performance and used life.
Comparative example 5 and embodiment are analyzed it is found that nonwoven cloth diaphragm not only good permeability, electrolyte can be improved by not absorbing water
Wellability also has antibiotic property, can prevent the erosion in the electrolytic solution such as bacterium, ensure the battery in long-term charge and discharge cycles
Quality so that ion passes through more unobstructed and have good electrical isolation.
The battery performance table made from above-described embodiment 1-4 and comparative example 1-5 as it can be seen that the battery of the embodiment of the present invention it is low
Warm discharge capacity sustainment rate, cycle characteristics are apparently higher than the scheme of comparative example.So the present invention uses low grain size and particle size dispersion
The positive electrode of narrow range is made positive and negative anodes pole piece by distinctive stirring coating process, and using nonwoven cloth diaphragm and adds
Add the electrolyte of low temperature additive.
Further, embodiment 1 prepares the cyclic curve under the conditions of battery 5C/1C as shown in Figure 1, after 25000 cycles
Discharge capacity sustainment rate 84%.Embodiment 1 prepares battery discharge curve under battery different temperatures as shown in Fig. 2, at -20 DEG C of temperature
Discharge capacity sustainment rate 74%, -43 DEG C of condition discharge capacity sustainment rates 59%.To sum up, battery of the present invention and its preparation
Method breaches restriction of the low temperature to lithium ion battery applications range significantly, the cycle with preferable cryogenic property and overlength
Performance.This not only can be with assisted electric vehicle in low temperature and severe cold area use, but also in the field vehicle of military industry field, smooth
Gram, field operation transport vehicle, the energy storage in frontier defense area and submarine, bathyscaphe, aircraft etc. require relatively high field also to have
Wide application space.
The above content in conjunction with specific embodiment to the present invention done be further elaborated on explanation, and it cannot be said that
The specific implementation of the present invention is only limitted to these explanations.For the those of ordinary skill of technical field of the present invention, not
Under the premise of being detached from present inventive concept, a number of simple deductions or replacements can also be made, is regarded as protection scope of the present invention.
Claims (10)
1. a kind of low temperature resistant extra long life lithium titanate battery, it is characterised in that：The anode of the lithium titanate battery used
Active material is a kind of powder with low grain size and particle size dispersion narrow range, and slurry granularity obtained is low after powder stirring, slurry
Pole piece surface density coherence request obtained is high after coating, low temperature additive is added in the electrolyte used, diaphragm is nonwoven
Cloth diaphragm.
2. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：Positive electrode active material
For ternary material, the weight percentage ranges of anode sizing agent：Positive 85%-98%, positive conductive agent 7%-1%, anode bond
Agent 8%-1%；Negative electrode active material is lithium titanate, the weight percentage ranges of negative electrode slurry：Cathode 87%-98%, negative conductive
Agent 1%-6%, negative electrode binder 1%-5%；Contain low temperature resistant additive in electrolyte.
3. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：The anode
Active material is ternary material LiNixCoyMnzO2, wherein x+y+z=1,0≤x, y, z≤0,2 μm≤D50≤8 μm of median particle diameter,
Particle size dispersion narrow range.
4. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：Positive conductive agent
For the mixture of one or both of carbon black, acetylene black, Super-P, KS-6, VGCF, positive electrode binder PVDF.
5. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：Negative electrode active material
For lithium titanate, cathode conductive agent is the mixture of one or both of carbon black, acetylene black, Super-P, KS-6, VGCF, cathode
Binder is PVDF.
6. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：The diaphragm
For nonwoven cloth diaphragm, thickness is 14-30 μm, porosity 45-72%, air penetrability 10-50cm3/sec。
7. a kind of low temperature resistant extra long life lithium titanate battery according to claim 1, it is characterised in that：The electrolysis
Low temperature resistant additive is added in liquid, is made of electrolyte and solvent, and wherein electrolyte is lithium hexafluoro phosphate, lithium perchlorate, trifluoro
One or more of pyrovinic acid lithium；Solvent is EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (carbonic acid diethyls
Ester), three kinds or a variety of in EMC (methyl ethyl carbonate), PC (propene carbonate) and VC (vinylene carbonate), but at least contain
PC and VC.
8. a kind of method preparing the low temperature resistant extra long life lithium titanate battery of claim 1-7 any one of them, feature
It is：Powder whipping process uses the agitating mode of high speed dispersion, to obtain high dispersing uniformity, slurry granularity obtained
It is low, size range D50≤15 μm.
9. a kind of method preparing the low temperature resistant extra long life lithium titanate battery of claim 1-7 any one of them, feature
It is：Slurry coating process should ensure that stability and precision, pole piece surface density error obtained are ± 2.5 ‰.
10. a kind of method preparing the low temperature resistant extra long life lithium titanate battery of claim 1-7 any one of them, feature
It is：The positive electrode, the negative electrode and the separator is made up of lamination or winding process.
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| CN110411913A (en) * | 2019-07-11 | 2019-11-05 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery separator coating size performance evaluation method |
| CN111564662A (en) * | 2020-06-29 | 2020-08-21 | 天津市捷威动力工业有限公司 | Method for improving low-temperature performance of lithium ion battery |
| CN114156446A (en) * | 2021-11-11 | 2022-03-08 | 珠海冠宇电池股份有限公司 | Negative electrode active material, negative plate containing negative electrode active material and lithium ion battery |
| EP3859860A4 (en) * | 2018-09-27 | 2022-09-21 | Murata Manufacturing Co., Ltd. | Lithium ion secondary battery |
| WO2023280104A1 (en) * | 2021-07-05 | 2023-01-12 | Damitz Thomas Gerhard Wilhelm | Battery cell for lithium ion battery |
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