CN109449446A - Secondary battery - Google Patents
Secondary battery Download PDFInfo
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- CN109449446A CN109449446A CN201811209263.8A CN201811209263A CN109449446A CN 109449446 A CN109449446 A CN 109449446A CN 201811209263 A CN201811209263 A CN 201811209263A CN 109449446 A CN109449446 A CN 109449446A
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- partial size
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a secondary battery, a pack thereofDraw together positive pole piece, negative pole piece, electrolyte and barrier film, positive pole piece includes the anodal mass flow body and sets up on the anodal mass flow body at least one surface and including the anodal active material's positive diaphragm, negative pole piece includes the negative mass flow body and sets up on the negative mass flow body at least one surface and including the negative active material's negative diaphragm. The secondary battery further satisfies: 1.0. ltoreq. CB/[ (D99)Negative pole‑D90Negative pole)/D50Negative pole]Less than or equal to 4.0. The invention obtains the secondary battery with long cycle life, high energy density and quick charging capability by matching the relationship between the battery capacity excess coefficient and the particle size distribution of the cathode active material.
Description
Technical field
The present invention relates to field of batteries more particularly to a kind of secondary cells.
Background technique
Rechargeable battery has the prominent spies such as light-weight, energy density is high, pollution-free, memory-less effect, long service life
Point, thus it is widely used in the fields such as mobile phone, computer, household electrical appliance, electric tool.Wherein, charging time and service life
Increasingly by the attention of terminal consumer, and the key factor that limitation rechargeable battery is universal.
How to obtain that take into account the battery of long circulation life and rapid charge characteristic be the problem generally faced in current industry.
Summary of the invention
In view of the problems in the background art, the purpose of the present invention is to provide a kind of secondary cells, can have both length
Cycle life, high-energy density and quick charge capability.
In order to achieve the above object, the present invention provides a kind of secondary cells comprising anode pole piece, cathode pole piece, electricity
Solve matter and isolation film, the anode pole piece include plus plate current-collecting body and be arranged at least one surface of plus plate current-collecting body and
Positive diaphragm including positive active material, the cathode pole piece include negative current collector and setting negative current collector at least
On one surface and the cathode membrane including negative electrode active material.The secondary cell also meets: 1.0≤CB/ [(D99It is negative-
D90It is negative)/D50It is negative]≤4.0.Wherein, CB is battery capacity excess coefficient；D50It is negativeIt is reached for negative electrode active material cumulative volume percentage
Corresponding partial size when to 50%, unit are μm；D90It is negativeIt is right when reaching 90% for negative electrode active material cumulative volume percentage
The partial size answered, unit are μm；D99It is negativeCorresponding partial size, unit when reaching 99% for negative electrode active material cumulative volume percentage
For μm.
Compared with the existing technology, the present invention is including at least as described below the utility model has the advantages that the present invention passes through match battery appearance
Measure the relationship between excess coefficient and negative electrode active material particle diameter distribution, obtained having both long circulation life, high-energy density with
And the secondary cell of quick charge capability.
Specific embodiment
The following detailed description of secondary cell according to the present invention.
Secondary cell of the invention includes anode pole piece, cathode pole piece, electrolyte and isolation film, the anode pole piece packet
It includes plus plate current-collecting body and is arranged at least one surface of plus plate current-collecting body and the positive diaphragm including positive active material, institute
Cathode pole piece is stated to include negative current collector and be arranged at least one surface of negative current collector and including negative electrode active material
Cathode membrane.
Secondary cell of the invention also meets: 1.0≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤4.0.Wherein, CB is battery
Capacity excess coefficient；D50It is negativeCorresponding partial size when reaching 50% for negative electrode active material cumulative volume percentage, unit are μm；
D90It is negativeCorresponding partial size when reaching 90% for negative electrode active material cumulative volume percentage, unit are μm；D99It is negativeIt is living for cathode
Property substance cumulative volume percentage reach partial size corresponding when 99%, unit is μm.
In certain embodiments of the present invention, CB/ [(D99It is negative-D90It is negative)/D50It is negative] lower limit value can for 1.0,1.1,
1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0, CB/ [(D99It is negative-D90It is negative)/D50It is negative] upper limit value can for 1.8,
1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0、3.1、3.2、3.3、3.4、3.5、3.6、3.7、
3.8,3.9,4.0.Preferably, 1.2≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤3.0；It is highly preferred that 1.5≤CB/ [(D99It is negative-
D90It is negative)/D50It is negative]≤2.5。
Inventor is the study found that the key of quickly charging battery capability improving is cathode, in quickly charging battery, such as
The potential minimum of fruit cathode on active ion reduction potential (such as lithium ion battery cathode potential minimum need
It is greater than 0V vs Li/Li+), then it is assumed that the dynamic performance of the cathode pole piece can satisfy the requirement of quickly charging battery.Together
Reason, in quickly charging battery, if the potential minimum of cathode, under active ion reduction potential, active ion can be preferential
It restores and is precipitated in negative terminal surface, rather than be embedded in negative electrode active material, think that the kinetics of cathode pole piece can at this time
Meet the requirement of quickly charging battery.Therefore, it is necessary to rationally design cathode charging potential.
Inventor has found that cathode charging potential size and battery capacity excess coefficient CB and cathode are lived by numerous studies
Property agent particle size distribution it is related.
The capacitance that active ion is subjected under the certain area of cathode pole piece is defined as M by weIt is negative, anode pole piece with
Cathode pole piece can provide active ion capacitance when having same area is defined as MJust, then battery capacity excess coefficient CB=
MIt is negative/MJust.From technical principle, battery capacity excess coefficient CB can by influence the practical Charging state of cathode (i.e. SOC) come
Influence cathode charging potential size.Battery capacity excess coefficient CB is bigger, and cathode is filled in high SOC during quickly charging battery
Electric potential is higher, and the reduction that cathode is less susceptible to occur active ion is precipitated, and volume expansion and the cathode pole of cathode pole piece
The side reaction of piece and electrolyte is also less, each contributes to promote quickly charging battery ability and cycle life；Conversely, same
Under the conditions of battery capacity excess coefficient CB it is smaller, cathode charging potential in high SOC is lower during quickly charging battery, cathode
The reduction for being more easy to happen active ion is precipitated, and quickly charging battery ability is also poorer.
In the negative active material, bulky grain negative electrode active material particle diameter distribution width and the close phase of cathode potential minimum
It closes.The more difficult insertion active ion of bulky grain negative electrode active material is also easier to that the reduction analysis of active ion occurs in cathode
Out, and bulky grain negative electrode active material particle diameter distribution is wider, illustrates bulky grain negative electrode active material in whole negative electrode active materials
In accounting it is more, cathode be more easy to happen active ion reduction be precipitated；But in the identical situation of other conditions, big
Grain negative electrode active material particle diameter distribution is wider, and negative electrode active material is easier to be compacted, and battery can obtain higher volume energy
Metric density.
Inventor has found by numerous studies, can use (D99It is negative-D90It is negative)/D50It is negativeCharacterize bulky grain negative electrode active material plasmid
The diameter dispersion of distribution, and when secondary cell meets 1.0≤CB/ [(D99It is negative-D90It is negative)/D50It is negativeWhen]≤4.0, in battery charging process
In, cathode charging potential is positively retained at more reasonable state, and cathode pole piece can have good dynamic performance, while secondary electricity
Pond can have both long circulation life, high-energy density and quick charge capability.
If CB/ [(D99It is negative-D90It is negative)/D50It is negative] > 4.0, the possible reason is CB is relatively large, (D99It is negative-D90It is negative)/D50It is negativePhase
(i.e. bulky grain negative electrode active material particle diameter distribution is narrow, bulky grain negative electrode active material is in whole negative electrode active materials to smaller
Accounting it is few), although both of which be conducive to promoted quickly charging battery ability, be detrimental to the compacting of cathode pole piece
Density, battery energy density loss are more.
If CB/ [(D99It is negative-D90It is negative)/D50It is negative] < 1.0, it may be possible to since bulky grain negative electrode active material particle diameter distribution is opposite
Wider, active ion insertion negative electrode active material becomes more difficult, and cathode potential minimum is smaller when charging, and cathode is easy to occur
The reduction of active ion is precipitated, therefore is unfavorable for realizing the promotion of quickly charging battery ability；It is also likely to be due to battery capacity
Excess coefficient CB design is relatively small, and cathode charging potential in high SOC is lower during quickly charging battery, and cathode also holds very much
The reduction that active ion easily occurs is precipitated, and is equally unfavorable for realizing the promotion of quickly charging battery ability.
In battery charging process, the particle diameter distribution of positive active material also will affect quickly charging battery ability.This is
Because liquid phase diffusion of the active ion inside porous electrode includes two parts, i.e., the liquid phase diffusion inside positive porous electrode
With the liquid phase diffusion inside cathode porous electrode.And active ion depends on liquid in the entire liquid phase diffusion kinetics of inside battery
Most difficult part is mutually spread, that is, there is short -board effect.It should be noted that liquid phase diffusion and active matter inside porous electrode
The particle diameter distribution width (i.e. (D90-D10)/D50) of matter entirety is related, and under equal conditions, the particle diameter distribution of active material entirety is got over
Width, then the liquid phase diffusion inside the active ion porous electrode is more difficult, this is because the particle diameter distribution of active material entirety is got over
Width, after active material particle collocation to porous electrode internal void to occupy ability stronger, in the active ion porous electrode
The liquid phase diffusional resistance in portion is bigger.
If the particle diameter distribution width of positive active material entirety and the particle diameter distribution width phase of negative electrode active material entirety
Difference is excessively greatly different, then active ion just will receive the limitation of some electrode in the liquid phase kinetics of diffusion of inside battery, cannot
Battery is set to reach optimum performance.Inventor is by a large amount of the study found that when secondary cell meets 0.5≤[(D90Just-D10Just)/
D50Just]/[(D90It is negative-D10It is negative)/D50It is negativeWhen]≤3.0, the particle diameter distribution matching of positive and negative electrode active material entirety reaches balance, electricity
Pond can obtain highest quick charge capability on the basis of not sacrifice energy density.
Wherein, D90JustAnd D90It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach corresponding when 90%
Partial size, unit be μm；D50JustAnd D50It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach 50% when institute
Corresponding partial size, unit are μm；D10JustAnd D10It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach 10%
When corresponding partial size, unit is μm.
In certain embodiments of the present invention, [(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negative] lower limit
Value can be 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5, [(D90Just-D10Just)/D50Just]/
[(D90It is negative-D10It is negative)/D50It is negative] upper limit value can for 1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,
2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0.Preferably, 1.0≤[(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/
D50It is negative]≤2.5。
As [(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negativeWhen] > 3.0, it may be possible to because of positive active material
Whole particle diameter distribution is relatively wide, is unfavorable for liquid phase diffusion of the active ion inside positive porous electrode at this time；When
[(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negativeWhen] < 0.5, it may be possible to because of the partial size of negative electrode active material entirety
Distribution is relatively wide, is unfavorable for liquid phase diffusion of the active ion inside cathode porous electrode at this time.
Preferably, the particle diameter distribution width of the positive active material entirety meets 0.8≤(D90Just-D10Just)/D50Just≤
4.0.Wherein, (D90Just-D10Just)/D50JustLower limit value can for 0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,
1.7,1.8,1.9,2.0, (D90Just-D10Just)/D50JustUpper limit value can for 1.8,1.9,2.0,2.1,2.2,2.3,2.4,
2.5,2.6,2.7,2.8,2.9,3.0,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4.0.It is highly preferred that described
The particle diameter distribution width of positive active material entirety meets 1.2≤(D90Just-D10Just)/D50Just≤3.5。
Preferably, the particle diameter distribution width of the negative electrode active material entirety meets 0.9≤(D90It is negative-D10It is negative)/D50It is negative≤
6.5.Wherein, (D90It is negative-D10It is negative)/D50It is negativeLower limit value can for 0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,
1.8,1.9,2.0, (D90It is negative-D10It is negative)/D50It is negativeUpper limit value can for 1.8,2.0,2.2,2.4,2.6,2.8,3.0,3.2,
3.4,3.6,3.8,4.0,4.2,4.5,4.8,5.0,5.2,5.5,5.8,6.0,6.2,6.5.It is highly preferred that the negative electrode active
The particle diameter distribution width of substance entirety meets 1.2≤(D90It is negative-D10It is negative)/D50It is negative≤4.5。
In secondary cell of the invention, it is preferable that the partial size D50 of the negative electrode active materialIt is negativeIt is 2 μm~18 μm；More
Preferably, the partial size D50 of the negative electrode active materialIt is negativeIt is 5 μm~15 μm.Preferably, the partial size of the negative electrode active material
D90It is negativeIt is 5 μm~40 μm；It is highly preferred that the partial size D90 of the negative electrode active materialIt is negativeIt is 10 μm~30 μm.Preferably, described negative
The partial size D99 of pole active materialIt is negativeIt is 10 μm~50 μm；It is highly preferred that the partial size D99 of the negative electrode active materialIt is negativeFor 15 μm~
50μm.Preferably, the partial size D10 of the negative electrode active materialIt is negativeIt is 1 μm~12 μm；It is highly preferred that the negative electrode active material
Partial size D10It is negativeIt is 4 μm~10 μm.
When the partial size of negative electrode active material is fallen into above-mentioned preferred scope, the homogeneity of cathode pole piece is higher, can be to avoid
Partial size is too small to be generated more side reaction and influences the improvement to battery performance with electrolyte, and partial size can also be avoided too big
Active ion solid phase inside anode active material particles is hindered to conduct and influence the improvement to battery performance.
In secondary cell of the invention, it is preferable that the partial size D10 of the positive active materialJustIt is 0.2 μm~6 μm；More
Preferably, the partial size D10 of the positive active materialJustIt is 0.4 μm~4.5 μm.Preferably, the partial size of the positive active material
D50JustIt is 0.8 μm~32 μm；It is highly preferred that the partial size D50 of the positive active materialJustIt is 1 μm~28 μm.Preferably, described
The partial size D90 of positive active materialJustIt is 1 μm~100 μm；It is highly preferred that the partial size D90 of the positive active materialJustFor 3 μm~
92μm。
When the partial size of positive active material is fallen into above-mentioned preferred scope, the homogeneity of anode pole piece is higher, can be to avoid
Partial size is too small to be generated more side reaction and influences the improvement to battery performance with electrolyte, and partial size can also be avoided too big
Active ion solid phase inside positive active material particle is hindered to conduct and influence the improvement to battery performance.
In secondary cell of the invention, it is preferable that the battery capacity excess coefficient CB is 0.8~2.0；More preferably
Ground, the battery capacity excess coefficient CB are 1.0~1.5.When battery capacity excess coefficient is fallen into above-mentioned preferred scope, battery
High-energy density advantage can be kept while preferably promoting quick charge capability.
In secondary cell of the invention, the cathode membrane be may be provided on one of surface of negative current collector
It can be set on two surfaces of negative current collector.The cathode membrane may also include conductive agent and binder, wherein leading
The type and content of electric agent and binder are not particularly limited, and can be selected according to actual needs.The negative pole currect collecting
The type of body is not also particularly limited, and can be selected according to actual needs.
In secondary cell of the invention, the anode diaphragm be may be provided on one of surface of plus plate current-collecting body
It can be set on two surfaces of plus plate current-collecting body.The anode diaphragm may also include conductive agent and binder, wherein leading
The type and content of electric agent and binder are not particularly limited, and can be selected according to actual needs.The anode collection
The type of body is not also particularly limited, and can be selected according to actual needs.
It should be noted that when positive diaphragm, cathode membrane are separately positioned on plus plate current-collecting body and negative current collector two
When on surface, as long as the plus plate current-collecting body wherein positive diaphragm on any one surface and negative current collector wherein any one table
Cathode membrane on face meets the present invention, that is, thinks that the battery is fallen within the scope of protection of the present invention.The present invention is given simultaneously
Each positive and negative electrode diaphragm parameters also refer both to the parameter of single side positive and negative electrode diaphragm.
Secondary cell of the invention can be lithium ion battery, can also be sodium-ion battery.
When secondary cell be lithium ion battery when: the positive active material can be selected from lithium and cobalt oxides, lithium nickel oxide,
Lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, olivine structural li-contained phosphate
Deng, but the present invention is not limited to these materials, other can also be used to be used as active substance of lithium ion battery anode
Conventional known material.One kind can be only used alone in these positive active materials, can also be used in combination of two or more.It is excellent
Selection of land, positive active material can be selected from LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2(NCM333)、
LiNi0.5Co0.2Mn0.3O2(NCM523)、LiNi0.6Co0.2Mn0.2O2(NCM622)、LiNi0.8Co0.1Mn0.1O2(NCM811)、
LiNi0.85Co0.15Al0.05O2、LiFePO4(LFP)、LiMnPO4One or more of.
When secondary cell is sodium-ion battery: the positive active material can be selected from transition metal oxide NaxMO2(M
For transition metal, be preferably selected from one or more of Mn, Fe, Ni, Co, V, Cu, Cr, 0 < x≤1), polyanionic material (phosphorus
Hydrochlorate, fluorophosphate, pyrophosphate, sulfate), Prussian blue material etc., but the application is not limited to these materials, this Shen
Other please can also be used to be used as the conventional known material of sodium-ion battery positive active material.These positive electrode active materials
One kind can be only used alone in matter, can also be used in combination of two or more.Preferably, positive active material can be selected from
NaFeO2、NaCoO2、NaCrO2、NaMnO2、NaNiO2、NaNi1/2Ti1/2O2、NaNi1/2Mn1/2O2、Na2/3Fe1/3Mn2/3O2、
NaNi1/3Co1/3Mn1/3O2、NaFePO4、NaMnPO4、NaCoPO4, Prussian blue material, general formula AaMb(PO4)cOxY3-xMaterial
(wherein A is selected from H to material+、Li+、Na+、K+、NH4+One or more of, M is transition-metal cation, be preferably selected from V, Ti, Mn,
One or more of Fe, Co, Ni, Cu, Zn, Y are halide anion, are preferably selected from one or more of F, Cl, Br, 0 < a
One or more of≤4,0 <b≤2,1≤c≤3,0≤x≤2).
In secondary cell of the invention, the specific type of the negative electrode active material is not particularly limited, can be according to reality
Border demand is selected.Preferably, the negative electrode active material can be selected from carbon material, silica-base material, tin-based material, in lithium titanate
One or more.Wherein, the carbon material can be selected from one of graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules
Or it is several；The graphite can be selected from one or more of artificial graphite, natural graphite；The silica-base material can be selected from simple substance
One or more of silicon, silicon oxide compound, silicon-carbon compound, silicon alloy；The tin-based material can be selected from simple substance tin, tin oxidation
Close one or more of object, tin alloy.It is highly preferred that the negative electrode active material in carbon material, silica-base material one
Kind is several.
In secondary cell of the invention, the isolation film is arranged between anode pole piece and cathode pole piece, plays isolation
Effect.Wherein, the type of the isolation film is not exposed to specific limitation, can be any isolation used in existing battery
Membrane material, such as polyethylene, polypropylene, Kynoar and their multilayer complex films, but it is not limited only to these.
In secondary cell of the invention, the type of the electrolyte is not exposed to specific limitation, can be liquid electric
It solves matter (also known as electrolyte), or solid electrolyte.Preferably, the electrolyte uses liquid electrolyte.Wherein, described
Liquid electrolyte includes electrolytic salt and organic solvent, and the specific type of electrolytic salt and organic solvent is not limited specifically
System, can be selected according to actual needs.The electrolyte may also include additive, and the additive types do not limit particularly
System can be cathode film for additive, can also be positive film for additive, or can improve adding for the certain performances of battery
Add agent, such as improves the additive of over-charging of battery performance, the additive that improves battery high-temperature behavior, improves battery cryogenic property
Additive etc..
Below by taking lithium ion battery as an example and in conjunction with specific embodiments, the application is further described.It should be understood that these implementations
Example is merely to illustrate the application rather than limitation scope of the present application.
Embodiment 1
(1) preparation of anode pole piece
Positive active material, conductive agent acetylene black, binder Kynoar (PVDF) 96:2:2 in mass ratio are carried out
Mixing is added solvent N-methyl pyrilidone (NMP), and stirring to system is in uniform shape under de-airing mixer effect, obtains just
Pole slurry；Anode sizing agent is coated uniformly on plus plate current-collecting body aluminium foil, room temperature is transferred to baking oven and continues drying after drying, then
By being cold-pressed, cutting to obtain anode pole piece.Wherein, see Table 1 for details for positive active material parameter.
(2) preparation of cathode pole piece
By negative electrode active material, conductive agent acetylene black, thickener sodium carboxymethylcellulose (CMC), binder butadiene-styrene rubber
(SBR) after the mixing of 96.4:1:1.2:1.4 in mass ratio, solvent deionized water is added, stirs under de-airing mixer effect to body
System is in uniform shape, obtains negative electrode slurry；Negative electrode slurry is coated uniformly on negative current collector copper foil, room temperature is transferred to after drying
Baking oven continues drying, then obtains cathode pole piece by cold pressing, cutting.Wherein, see Table 1 for details for negative electrode active material parameter.
(3) preparation of electrolyte
Ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) are carried out according to 1:1:1 by volume
It is mixed to get organic solvent, then by sufficiently dry lithium salts LiPF6It is dissolved in mixed organic solvent, is configured to concentration
For the electrolyte of 1mol/L.
(4) preparation of isolation film
Select polyethylene film as isolation film.
(5) preparation of lithium ion battery
Above-mentioned anode pole piece, isolation film, cathode pole piece are folded in order, are in isolation film between positive and negative electrode pole piece
Play the role of isolation, then winding obtains naked battery core；Naked battery core is placed in outer packing shell, injects electrolyte after dry, is passed through
The processes such as Vacuum Package, standing, chemical conversion, shaping are crossed, lithium ion battery is obtained.
The lithium ion battery of embodiment 2-24 and comparative example 1-6 are prepared according to method similar to Example 1,
Specific difference is shown in table 1.
Table 1: the parameter of embodiment 1-24 and comparative example 1-6
The performance test of battery will be illustrated next.
1, pole piece is tested
(1) the partial size test of positive and negative electrode active material
The partial size of positive and negative electrode active material can be by using laser diffraction granularity distribution measuring apparatus (Mastersizer
3000) test obtains.
(2) battery capacity excess coefficient CB is tested
1. the capacitance of unit area anode pole piece is tested
Step 1): the battery containing each embodiment and the anode pole piece of comparative example is completely put, and is stood after five minutes, is charged to
Blanking voltage, wherein charging process is specially with 1/3C constant-current charge to blanking voltage, then again with blanking voltage constant-voltage charge
To 0.03C, the charging capacity C at this time obtained0The as discharge capacity of anode pole piece.
Step 2): measuring and calculates the gross area of positive diaphragm (gross area herein refers to spreading area；If two-sided painting
The spreading area on two sides need to be added by cloth).
Step 3): according to capacitance=anode pole piece discharge capacity (mAh) of unit area anode pole piece/anode diaphragm
The gross area (cm2), the capacitance M of unit area anode pole piece is calculatedJust。
2. the capacitance of unit area cathode pole piece is tested
Step 1): taking the cathode pole piece of the various embodiments described above and comparative example, is obtained using Lamination mould certain area, single
The cathode sequin of face coating.It is to electrode, Celgard film as isolation film, dissolved with LiPF using metal lithium sheet6(concentration 1mol/
L the solution of EC+DMC+DEC (volume ratio 1:1:1)) is electrolyte, and 6 CR2430 types are assembled in the glove box of argon gas protection
Button cell.Button batteries stand 12h after installing, and constant-current discharge is carried out under the discharge current of 0.05C, until voltage is
Then 5mV carries out constant-current discharge with the discharge current of 50 μ A again, until voltage be 5mV, then carried out with the discharge current of 10 μ A
Constant-current discharge, until voltage is 5mV, standing 5 minutes finally carries out constant-current charge, until final under the charging current of 0.05C
Voltage is 2V, records charging capacity.The average value of 6 button cell charging capacitys is the average capacitance amount of cathode pole piece.
Step 2): using the diameter d of calliper to measure cathode sequin, and the area of cathode sequin is calculated.
Step 3): according to the capacitance of unit area cathode pole piece=cathode sequin average capacitance amount (mAh)/cathode
Area (the cm of sequin2), the capacitance M of unit area cathode pole piece is calculatedIt is negative。
3. battery capacity excess coefficient CB=MIt is negative/MJust。
2, battery testing
(1) dynamic performance is tested
At 25 DEG C, after the battery that embodiment and comparative example is prepared completely is filled with x C, is completely put and is repeated 10 times with 1C,
Battery is completely filled with x C again, then disassembles out cathode pole piece, and observes cathode pole piece surface analysis lithium situation.If negative terminal surface
Lithium is not analysed, then rate of charge x C is incremented by using 0.1C as gradient and is tested again, until negative terminal surface analyses lithium, stops test,
Rate of charge x C at this time subtracts the maximum charge multiplying power that 0.1C is battery.
(2) cycle performance is tested
At 25 DEG C, the battery that embodiment and comparative example is prepared is charged with 3C multiplying power, with 1C multiplying power discharging, is carried out
Full be full of puts loop test, until the capacity of battery is less than the 80% of initial capacity, records circulating ring number.
(3) actual energy density measurement
At 25 DEG C, the battery that embodiment and comparative example is prepared completely is filled with 1C multiplying power, is completely put with 1C multiplying power, recorded
Actual discharge energy at this time；At 25 DEG C, weighed using electronic balance to the battery；Battery 1C actual discharge energy with
The ratio of battery weight is the actual energy density of battery.
Wherein, when actual energy density is less than the 80% of target energy density, it is believed that battery actual energy density is very low；
When actual energy density is more than or equal to the 80% of target energy density and is less than the 95% of target energy density, it is believed that battery is practical
Energy density is relatively low；Actual energy density is more than or equal to the 95% of target energy density and is less than the 105% of target energy density
When, it is believed that battery actual energy medium density；Actual energy density is more than or equal to the 105% of target energy density and is less than target
Energy density 120% when, it is believed that battery actual energy density is higher；Actual energy density is the 120% of target energy density
When above, it is believed that battery actual energy density is very high.
Table 2: the performance test results of embodiment 1-24 and comparative example 1-6
From the test result of table 2 it can be seen that the battery of embodiment 1-24 is all satisfied 1.0≤CB/ [(D99It is negative-D90It is negative)/
D50It is negative]≤4.0, battery capacity excess coefficient CB and bulky grain negative electrode active material particle diameter distribution width (D99It is negative-D90It is negative)/D50It is negative
Matching relationship is good, and cathode charging potential is positively retained at more reasonable state when quickly charging battery, and cathode pole piece can have good
Good dynamic performance, the battery obtained from can have both long circulation life, high-energy density and quick charge capability.
Compared with embodiment 1-24, battery capacity excess coefficient CB and bulky grain negative electrode active material plasmid in comparative example 1-6
The diameter dispersion of distribution (D99It is negative-D90It is negative)/D50It is negativeFail to reach Proper Match, CB/ [(D99It is negative-D90It is negative)/D50It is negative] not in given model
In enclosing, battery can not have both long circulation life, high-energy density and quick charge capability simultaneously.
Further, the partial size D50 of negative electrode active materialIt is negativePreferably 2 μm~18 μm, D90It is negativePreferably 5 μm~40 μm, D99It is negative
Preferably 10 μm~50 μm, when the partial size of negative electrode active material is fallen into above-mentioned preferred scope, the homogeneity of cathode pole piece is higher,
More side reaction can be generated with electrolyte and influence the improvement to battery performance, can also avoid to avoid partial size is too small
Partial size is too big to hinder lithium ion solid phase inside anode active material particles to conduct and influence the improvement to battery performance.Electricity
Tankage excess coefficient CB is preferably 0.8~2.0, and when battery capacity excess coefficient is fallen into above-mentioned preferred scope, battery can be with
High-energy density advantage is kept while preferably promoting quick charge capability.
But work as the partial size D50 of negative electrode active materialIt is negative、D90It is negative、D99It is negativeAnd one in battery capacity excess coefficient CB
Or several parameters are not when being able to satisfy above-mentioned preferred scope, as long as guaranteeing 1.0≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤4.0, reference
Embodiment 17-20, battery remain to have both long circulation life, high-energy density and quick charge capability.
Further, under the premise of cathode pole piece has excellent dynamic performance, by rationally adjusting positive and negative electrode activity
The ratio of the particle diameter distribution width of substance entirety, makes battery also meet 0.5≤[(D90Just-D10Just)/D50Just]/[(D90It is negative-
D10It is negative)/D50It is negativeWhen]≤3.0, battery can obtain higher quick charge capability while not sacrifice energy density.
In conjunction with the embodiments 19, [(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negative] < 0.5, negative electrode active material is whole
The particle diameter distribution of body is relatively wide, is unfavorable for liquid phase diffusion of the lithium ion inside cathode porous electrode, that is, is unfavorable for lithium ion
Fast transferring is embedded in cathode, therefore compared with other embodiments, embodiment 19 is relatively weak to quickly charging battery capability improving.
11, embodiment 20 in conjunction with the embodiments, [(D90Just-D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negative] > 3.0, anode
The particle diameter distribution of active material entirety is relatively wide, is unfavorable for liquid phase diffusion of the lithium ion inside positive porous electrode, also anticipates
Taste be unfavorable for lithium ion fast transferring insertion cathode, therefore compared with other embodiments, embodiment 11, embodiment 20 are to battery
Quick charge capability is promoted relatively weak.
From embodiment 21-24 and comparative example 3-6 it is found that when the different positive and negative electrode active material of Selection of Battery, only
Battery is wanted to meet 1.0≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤4.0, can also have both long circulation life, high-energy density and
Quick charge capability.
According to the disclosure and teachings of the above specification, those skilled in the art can also change above embodiment
And modification.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to some modifications of the invention and
Change should also be as falling into the scope of the claims of the present invention.In addition, although having been used in this specification some specific
Term, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of secondary cell, including anode pole piece, cathode pole piece, electrolyte and isolation film, the anode pole piece includes just
Pole collector and it is arranged at least one surface of plus plate current-collecting body and the positive diaphragm including positive active material, it is described negative
Pole pole piece includes negative current collector and is arranged in negative at least one surface of negative current collector and including negative electrode active material
Pole diaphragm；
It is characterized in that,
The secondary cell meets: 1.0≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤4.0；
Wherein,
CB is battery capacity excess coefficient；
D50It is negativeCorresponding partial size when reaching 50% for negative electrode active material cumulative volume percentage, unit are μm；
D90It is negativeCorresponding partial size when reaching 90% for negative electrode active material cumulative volume percentage, unit are μm；
D99It is negativeCorresponding partial size when reaching 99% for negative electrode active material cumulative volume percentage, unit are μm.
2. secondary cell according to claim 1, which is characterized in that
The secondary cell meets: 1.2≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤3.0；
Preferably, the secondary cell meets: 1.5≤CB/ [(D99It is negative-D90It is negative)/D50It is negative]≤2.5。
3. secondary cell according to claim 1, which is characterized in that the secondary cell also meets: 0.5≤[(D90Just-
D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negative]≤3.0；
Wherein,
D90JustAnd D90It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach partial size corresponding when 90%, single
Position is μm；
D50JustAnd D50It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach partial size corresponding when 50%, single
Position is μm；
D10JustAnd D10It is negativeRespectively anode and negative electrode active material cumulative volume percentage reach partial size corresponding when 10%, single
Position is μm.
4. secondary cell according to claim 3, which is characterized in that the secondary cell also meets: 1.0≤[(D90Just-
D10Just)/D50Just]/[(D90It is negative-D10It is negative)/D50It is negative]≤2.5。
5. secondary cell according to claim 3 or 4, which is characterized in that the negative electrode active material meets 0.9≤
(D90It is negative-D10It is negative)/D50It is negative≤ 6.5, it is preferable that 1.2≤(D90It is negative-D10It is negative)/D50It is negative≤4.5。
6. secondary cell according to claim 3 or 4, which is characterized in that the positive active material meets 0.8≤
(D90Just-D10Just)/D50Just≤ 4.0, it is preferable that 1.2≤(D90Just-D10Just)/D50Just≤3.5。
7. secondary cell according to claim 1 or 2, which is characterized in that the battery capacity excess coefficient CB be 0.8~
2, preferably 1.0~1.5.
8. secondary cell described in any one of -4 according to claim 1, which is characterized in that
The partial size D10 of the negative electrode active materialIt is negativeIt is 1 μm~12 μm, preferably 4 μm~10 μm；
And/or the partial size D50 of the negative electrode active materialIt is negativeIt is 2 μm~18 μm, preferably 5 μm~15 μm；
And/or the partial size D90 of the negative electrode active materialIt is negativeIt is 5 μm~40 μm, preferably 10 μm~30 μm；
And/or the partial size D99 of the negative electrode active materialIt is negativeIt is 10 μm~50 μm, preferably 15 μm~50 μm.
9. secondary cell according to claim 3 or 4, which is characterized in that
The partial size D10 of the positive active materialJustIt is 0.2 μm~6 μm, preferably 0.4 μm~4.5 μm；
And/or the partial size D50 of the positive active materialJustIt is 0.8 μm~32 μm, preferably 1 μm~28 μm；
And/or the partial size D90 of the positive active materialJustIt is 1 μm~100 μm, preferably 3 μm~92 μm.
10. secondary cell according to claim 1 or 3, which is characterized in that
The negative electrode active material is selected from one or more of carbon material, silica-base material, tin-based material, lithium titanate；
Preferably, the negative electrode active material is selected from one or more of carbon material, silica-base material.
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