CN106848379A - Electrode of lithium secondary cell containing hygroscopic matter and the lithium secondary battery comprising it - Google Patents
Electrode of lithium secondary cell containing hygroscopic matter and the lithium secondary battery comprising it Download PDFInfo
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- CN106848379A CN106848379A CN201610997975.5A CN201610997975A CN106848379A CN 106848379 A CN106848379 A CN 106848379A CN 201610997975 A CN201610997975 A CN 201610997975A CN 106848379 A CN106848379 A CN 106848379A
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- active material
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- lithium secondary
- hygroscopic matter
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of 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
- 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
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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
Abstract
Electrode of lithium secondary cell and lithium secondary battery comprising it the present invention relates to contain hygroscopic matter, electrode of lithium secondary cell between being related to hygroscopic matter to be located at the space for being arranged and being formed by above-mentioned active material in active material layer, in electrode of lithium secondary cell of the invention, between hygroscopic matter is located at the space formed by active material in active material layer, it is thus able to remove the moisture for being present in electrode and electrolyte, so as to exclude the side reaction because there is moisture and causing in battery, thus, it is possible to improve battery performance.
Description
Technical field
The present invention relates to the electrode of lithium secondary cell containing hygroscopic matter and the lithium secondary battery comprising it, in more detail
Ground, is related to improve comprising the hygroscopic materials for being used for the fine moisture for removing electrode the secondary lithium batteries of battery performance
Electrode and the lithium secondary battery comprising it.
Background technology
With technological development and increase in demand to mobile device, the demand to the secondary cell as the energy is also positive anxious
Increase severely and add.In this secondary cell, show high-energy-density and operating potential, have extended cycle life, the lithium that self-discharge rate is low
Secondary cell is by commercialization and is widely utilized.
Also, in recent years, as the attention rate to environmental problem is improved, to that can substitute as the master for causing atmosphere pollution
Gasoline vehicle, diesel vehicle of one of reason etc. are wanted using the vehicle of fossil fuel, such as to electric automobile (EV), hybrid power electricity
The research of electrical automobile (HEV) carries out more.As the dynamic of this electric automobile (EV), mixed power electric car (HEV) etc.
Power source, it is main to use ni-mh metal (Ni-MH) secondary cell, but to using with high-energy-density, discharge voltage high and output
Research in terms of the lithium secondary battery of stability is just actively carried out, and part commercialization.
Lithium secondary battery is formed by the structure that the nonaqueous electrolytic comprising lithium salts impregnated in electrode assemblie, in above-mentioned electrode
In component, porous seperation film is between the positive pole (positive for being coated with active material on electrode collector respectively
Electrode) and negative pole (negative electrode) between.
In the case where moisture is contained in the inside of this lithium secondary battery, this is likely to become the reason for reducing battery performance.
In the lithium secondary battery, moisture may be contained in the inside of active material during manufacturing process, or may be with micro presence
Form is contained in electrolyte.For example, the Li-Ti oxide as negative electrode active material during charging and discharging because structure become
Change extremely low zero deformation rate (zero-strain) material and life characteristic is very excellent, and form voltage section relatively high, and
Ingotism (dendrite) is not produced, thus it is very excellent as security (safety) and stability (stability)
Material be widely known by the people, also, there is the used in rapid charging pole characteristic that can be charged in moisture, but because
Due to the property of moisture in absorption air, in the case of using above-mentioned Li-Ti oxide to manufacture electrode, exist because contained
Moisture be decomposed and produce the problem of a large amount of gases.
Also, the moisture for existing in the electrolytic solution occurs anti-by the electrical potential energy provided in charging process with electrolyte
Should, it is possible to producing gas and causing phenomenon of cell expansion etc., the reliability of battery may be reduced.For example, electrolyte
Comprising LiPF6Lithium salts and water react and are formed as the HF of strong acid, the HF for being formed actively with show alkalescent
Electrode active material react and dissolution electrode active material composition, as a result, cause the degeneration of battery, and just
Pole surface forms lithium fluoride (LiF) to increase the resistance in electrode, and produces gas, so as to the life-span for causing battery declines.
Thus, various methods are utilized for the moisture removed inside lithium secondary battery, for example, in order to remove the secondary electricity of lithium
The moisture of the electrode in pond, the moisture of electrode is removed by high temperature drying operation, also, sharp in order to remove the moisture of electrolyte
Method (Korean Patent Publication No. 2015-0037332) used in the configuration hygroscopic material such as battery case etc..
But, only cannot be by the moisture removal of electrode to desired degree, so that exploitation one by the above method
Plant the new technology that can improve battery performance by more effectively removing the moisture of electrode.
The content of the invention
Problem to be solved by this invention is, there is provided be possibly comprised in due to effectively being removed containing hygroscopic matter
The electrode of lithium secondary battery and the moisture of electrolyte are so as to improve the electrode of lithium secondary cell of battery performance.
Another problem to be solved by this invention is, there is provided the secondary lithium batteries containing hygroscopic matter as described above
The manufacture method of electrode.
According to an embodiment, the present invention provides following electrode of lithium secondary cell, i.e. electrode of lithium secondary cell is included
Active material layer and collector, above-mentioned active material layer include active material and hygroscopic matter, and above-mentioned hygroscopic matter is upper
State between the space for being located in active material layer and being formed by above-mentioned active material.
According to another embodiment, the present invention provides the manufacture method of following electrode of lithium secondary cell, i.e. the secondary electricity of lithium
The manufacture method of pond electrode includes：Step (1), applies active material is formed containing the slurry of active material on the current collector
Layer；And step (2), the dispersion liquid containing hygroscopic matter is permeated in above-mentioned active material layer, so that above-mentioned hygroscopicity
Material is located between the space for being arranged and being formed by above-mentioned active material.
In active material layer, hygroscopic matter is located at what is formed by active material to electrode of lithium secondary cell of the invention
Between space, it is thus possible to removal moisture present in electrode and electrolyte such that it is able to exclude because there is water in battery
The side reaction for dividing and causing, thus, it is possible to improve battery performance.
Brief description of the drawings
Fig. 1 is located at the space formed by active material arrangement to be schematically illustrated in hygroscopic matter in active material layer
Between form figure.
Fig. 2 is to schematically show that hygroscopic matter is located at the figure of the form of active material surface.
Fig. 3 is the figure for schematically showing the form that hygroscopic matter is located between active material and collector.
Fig. 4 is to represent make the battery and comparative example 1-1 of embodiment 1-1 to embodiment 19-1 to comparative example 3-1 respectively
Battery by 100 times circulate after the measurement result being measured to the capacity sustainment rate of battery chart.
Specific embodiment
Hereinafter, in order to help to understand the present invention, the present invention is illustrated in greater detail.
Term used in this specification and the claimed scope of invention should not be with the implication in routine or dictionary
To limit and explain, but the concept of term can be fitted to illustrate its invention in optimal method based on inventor
The principle that locality is defined, is explained with meeting the implication and concept of the technology of the present invention thought.
Electrode of lithium secondary cell of the invention includes active material layer and collector, and above-mentioned active material layer includes activity
Material and hygroscopic matter, above-mentioned hygroscopic matter are located in above-mentioned active material layer and are arranged by above-mentioned active material and formed
Space between.
The moisture of executable moisture, the moisture of such as electrode and the electrolyte to being included in battery of above-mentioned hygroscopic matter
Etc. the function of being absorbed and removed, due between the space for being arranged and being formed by above-mentioned active material, thus will not produce
Life makes the overall volume of active material layer become problem that is big and reducing the energy density of per unit volume.
Above-mentioned hygroscopic matter can be enumerated selected from by silica gel, zeolite, CaO, BaO, MgSO4、Mg(ClO4)2、MgO、P2O5、
Al2O3、CaH2、NaH、LiAlH4、CaSO4、Na2SO4、CaCO3、K2CO3、CaCl2, 4A molecular sieves and 3A molecular sieves, Ba
(ClO4)2, one or more of group of poly- (acrylic acid) and poly- (acrylic acid) composition for combining of crosslinking, specifically, can be selected from
By silica gel, zeolite, P2O5And Al2O3One or more of group of composition.
Above-mentioned active material can have 0.1 μm to 30 μm of average grain diameter (D50), specifically, there can be 0.5 μm to 10 μm
Average grain diameter, more specifically, 1 μm to 5 μm of average grain diameter can be had.
When above-mentioned active material has 0.1 μm to 30 μm of average grain diameter (D50) when, arranged and shape by above-mentioned active material
Into space can have 0.01 μm to 20 μm of size, specifically, can have 0.03 μm to 10 μm of size, more specifically, can
With 0.05 μm to 5 μm of size.Now, when assuming that there is ball with its inscribe in above-mentioned space, above-mentioned space it is big
I is represented by the particle diameter of above-mentioned ball.
Above-mentioned hygroscopic matter can be in the way of it can be included in the space for being arranged and being formed by above-mentioned active material
With 10nm to 20 μm of average grain diameter (D50), specifically, there can be 30nm to 10 μm of average grain diameter (D50), more specifically,
There can be 50nm to 5 μm of average grain diameter (D50)。
The size of above-mentioned hygroscopic matter can be directly proportional to the size of above-mentioned active material, for example, above-mentioned hygroscopicity thing
Average grain diameter (D of the matter relative to above-mentioned active material50) there can be 0.1% to 70% average grain diameter (D50) size, specifically
Ground, the average grain diameter (D can with 1% to 67%50) size, more specifically, 5% to 50% average grain diameter (D can be had50)
Size.
Have more than 0.1% average grain diameter big relative to the average grain diameter of above-mentioned active material in above-mentioned hygroscopic matter
In the case of small, fill with being prevented from above-mentioned hygroscopic matter tight the space that is arranged and formed by above-mentioned active material from
And the problem of the passage that electrolyte can impregnate is blocked, in average grain diameter of the above-mentioned hygroscopic matter relative to above-mentioned active material
In the case of with less than 70% Average Particle Diameters, following problem is prevented from：Above-mentioned hygroscopic matter becomes than above-mentioned
The size in space is located at the part outside space greatly, or hinders the contact between above-mentioned active material, or increase active material layer
Overall volume and reduce the energy density of per unit density.
In the present invention, above-mentioned average grain diameter (D50) particle diameter under 50% benchmark of particle diameter distribution can be defined as.It is above-mentioned
Average grain diameter is not particularly limited, for example, using laser diffractometry (laser diffraction method) or scanning electron
Microscope (SEM) photo is determined.Above-mentioned laser diffractometry can be generally determined from sub-micron (submicron) field to several mm
The particle diameter of degree, can obtain the result with high reproducibility and high de-agglomeration.
On the basis of the above-mentioned active material of 100 weight portions, above-mentioned hygroscopic matter can include 1 weight portion to 20 weight
Part, it is preferable that can be comprising 2 weight portions to 10 weight portions, it is highly preferred that 3 weight portions to 7 weight portions can be included.
If the content of above-mentioned hygroscopic matter is more than 1 weight portion on the basis of the above-mentioned active material of 100 weight portions,
Appropriate moisture sorption effect can be showed, if below 20 weight portions, then following problem can be prevented：The space of above-mentioned active material layer
Can excessively reduce, or above-mentioned hygroscopic matter hinders the contact between above-mentioned active material, or make the overall body of active material layer
Product increases and reduces the energy density of per unit density.
Above-mentioned hygroscopic matter can be the mixing that 2 kinds of hygroscopic matters by being classified according to particle size are mixed
Thing, specifically, the mixture of above-mentioned hygroscopic matter can be that the first relatively large hygroscopic matter of size and size are relatively small
The second hygroscopic matter mixture.
In this way, mixed comprising the first relatively large hygroscopic matter of size and the second relatively small hygroscopic matter of size
In the case of compound, above-mentioned hygroscopic matter can be more efficiently located in the space between above-mentioned active material such that it is able to
The energy for suppressing to occur the overall volume increase thus per unit density because of the active material layer comprising above-mentioned hygroscopic matter is close
Spend the phenomenon for reducing.
Above-mentioned first hygroscopic matter can have 1 μm to 20 μm of average grain diameter (D50), specifically, there can be 5 μm to 20 μ
Average grain diameter (the D of m50), more specifically, 5 μm to 10 μm of average grain diameter (D can be had50), above-mentioned second hygroscopic matter can
With 10nm to 1 μm of average grain diameter (D50), specifically, there can be the average grain diameter (D of 20nm to 500nm50), more specifically,
There can be the average grain diameter (D of 50nm to 300nm50)。
Now, the first hygroscopic matter and the second hygroscopic matter can be with 60:40 to 99:1 weight ratio mixes, and has
Body ground, can be with 70:30 to 98:2 weight ratio mixes, more specifically, can be with 80:20 to 95:5 weight ratio is mixed
Close.
In the case where the weight ratio of the first hygroscopic matter and the second hygroscopic matter meets above range, can suppress
The volume increase of active material layer, and hygroscopic matter is uniformly dispersed, and moisture sorption effect is further improved, moisture absorption can be prevented
Property material hinder electrolyte permeability.
The specific species of above-mentioned first hygroscopic matter and the second hygroscopic matter with identical or different, but be able to can lead to
Cross the species that is combined as the first hygroscopic matter and the second hygroscopic matter and moisture sorption effect is more maximized.
In one of the invention, above-mentioned first hygroscopic matter can be selected from by silica gel, zeolite, 4A molecular sieves and 3A
One or more of group of poly- (acrylic acid) and poly- (acrylic acid) composition that molecular sieve, crosslinking are combined, above-mentioned second hygroscopicity
Material can be selected from by CaO, BaO, MgSO4、Mg(ClO4)2、MgO、P2O5、Al2O3、CaH2、NaH、LiAlH4、CaSO4、
Na2SO4、CaCO3、K2CO3And Ba (ClO4)2One or more of group of composition, specifically, above-mentioned first hygroscopic matter can be with
It is selected from by silica gel, zeolite, BaO and MgSO4One or more of group of composition, above-mentioned second hygroscopic matter can be selected from
By MgO, P2O5And Al2O3One or more of group of composition.
The active material layer of above-mentioned electrode of lithium secondary cell can include active material and hygroscopic matter, and have
10% to 40% voidage, specifically, can have 20% to 30% voidage, more specifically, 25% to 30% can be had
Voidage.
In the case where the voidage of active material layer meets above range, electrolyte can be made suitably to permeate, can obtained
More excellent moisture sorption effect.
The method for making above-mentioned hygroscopic matter be located between the space for being arranged and being formed by above-mentioned active material is not limited especially
It is fixed, for example, can realize by the following method, i.e. the above method includes：Step (1), on the current collector coating contains active matter
The slurry of matter forms active material layer；And step (2), the dispersion liquid containing hygroscopic matter is permeated in above-mentioned active matter
Matter layer, and above-mentioned hygroscopic matter is located between the space for being arranged and being formed by above-mentioned active material.
Now, above-mentioned slurry can as needed to be contained in above-mentioned active material layer active material add bonding agent,
Conductive agent and mixed with solvent and to be prepared.Above-mentioned active material layer can be additionally carried out making above-mentioned dispersion liquid permeate it
The step for being compressed afterwards and drying, can carry out preferentially being dried before above-mentioned dispersion liquid permeates the step of above-mentioned active material layer
Suddenly.By method as described above, can make above-mentioned hygroscopic matter be located at the space that is arranged and formed by above-mentioned active material it
Between, it is illustrated schematically in Fig. 1.
As needed, above-mentioned hygroscopic matter can also be located at outside above-mentioned space, for example, may be located at above-mentioned active matter
Above-mentioned hygroscopic matter is configured between the surface of matter, above-mentioned active material layer and collector or in these positions.In this way,
In the case of above-mentioned hygroscopic matter is located at outside space, hygroscopic matter is eventually set also to be configured at the activity of above-mentioned electrode
Outside the space of material layer, thus the presence of more dispersed hygroscopic matter can be played and effectively absorb electric pool inner water
The effect divided, but the presence of the hygroscopic matter outside above-mentioned space may cause the overall volume of active material layer to increase
Greatly, so that suitably adjusting the amount of above-mentioned hygroscopic matter.Above-mentioned hygroscopic matter is diagrammatically illustrated in fig. 2 to be located at
The form of above-mentioned active material surface, diagrammatically illustrates above-mentioned hygroscopic matter positioned at above-mentioned active material and collection in figure 3
Form between electric body.
Above-mentioned hygroscopic matter is set to be located between the space for being arranged and being formed by above-mentioned active material and above-mentioned active material
The method on surface is not particularly limited, for example, can realize by the following method, i.e. the above method includes：Step (1), in current collection
The slurry containing active material is applied on body to form active material layer；And step (2), by the dispersion containing hygroscopic matter
Liquid is permeated in above-mentioned active material layer, and make above-mentioned hygroscopic matter be located at the space that is arranged and formed by above-mentioned active material it
Between, before above-mentioned steps (1), additionally including carrying out dry-mixing (dry to above-mentioned active material and hygroscopic matter
Mixing) or hard mixing (hard mixing) and the step of above-mentioned hygroscopic matter is close to above-mentioned active material surface.
Above-mentioned dry-mixing can mix above-mentioned active material without bonding agent or thickener etc. and hygroscopic matter comes
Realize, it is above-mentioned it is hard be blended in there is very small amount bonding agent or thickener etc. in the case of mix above-mentioned active material at high viscosities
Realized with hygroscopic matter.
Now, positioned at the hygroscopic matter in the space for being arranged and being formed by above-mentioned active material and positioned at above-mentioned active material
The hygroscopic matter on surface can have 99.9:0.1 to 80:20 weight ratio, specifically, can have 99.5:0.5 to 90:10
Weight ratio, more specifically, 99 can be had:1 to 95:5 weight ratio.
On the other hand, it is located at above-mentioned hygroscopic matter between the space for being arranged and being formed by above-mentioned active material and above-mentioned
Method between active material and collector is not particularly limited, for example, can realize by the following method, i.e. the above method can
Including：Step (1), applies the slurry containing active material to form active material layer on the current collector；And step (2), will
Dispersion liquid containing hygroscopic matter is permeated in above-mentioned active material layer, and above-mentioned hygroscopic matter is located at by above-mentioned active matter
Between the space that matter is arranged and formed, before above-mentioned steps (1), additionally including coating on above-mentioned collector makes hygroscopicity
The step of material and bonding agent are mixed in the mixture of solvent.As needed, the mixture for being coated on above-mentioned collector can
Additionally comprising conductive agent etc., being contained in the amount of the hygroscopic matter of each position can be by used in each step
The amount of hygroscopic matter be suitably adjusted and adjusted.
Above-mentioned hygroscopic matter between the space for being arranged and being formed by above-mentioned active material be located at above-mentioned activity
Above-mentioned hygroscopic matter between material and collector can have 99.9:0.1 to 80:20 weight ratio, specifically, can have
99.5:0.5 to 90:10 weight ratio, more specifically, 99 can be had:1 to 95:5 weight ratio.
The above-mentioned hygroscopic matter is located between the space for being arranged and being formed by above-mentioned active material, above-mentioned active material
Method between surface and above-mentioned active material and collector is not particularly limited, for example, can realize by the following method, i.e.
The above method includes：Step (1), dry-mixing or hard mixing is carried out to active material and hygroscopic matter and makes above-mentioned hygroscopicity thing
Matter is close to the surface of above-mentioned active material；And step (2), will obtain from the above-mentioned steps (1) containing being close on surface
There is the slurry coating of active material of hygroscopic matter in active material layer is formed on collector, before above-mentioned steps (2),
Additionally include the step of coating makes hygroscopic matter and bonding agent be mixed in the mixture of solvent on above-mentioned collector.
As needed, the mixture for being coated on above-mentioned collector additionally comprising conductive agent etc. can be contained in the hygroscopicity of each position
The amount of material can be suitably adjusted and adjusted by the amount to the hygroscopic matter used in each step.
Between the space for being arranged and being formed by above-mentioned active material, the surface of above-mentioned active material and above-mentioned active matter
Above-mentioned hygroscopic matter between matter and collector can have 99.9:0.05:0.05 to 80:10:10 weight ratio, specifically,
Can have 99.5:0.25:0.25 to 90:5:5 weight ratio, more specifically, 99 can be had:0.5:0.5 to 95:2.5:2.5
Weight ratio.
As described above, when outside above-mentioned hygroscopic matter is also located at above-mentioned space, the amount of above-mentioned hygroscopic matter is relative
Can have 99.9 in the hygroscopic matter positioned at above-mentioned space:0.1 to 80:20 weight ratio, outside above-mentioned space
The amount of hygroscopic matter is relative to the situation that 99.9 weight portions of the hygroscopic matter positioned at above-mentioned space are more than 0.1 weight portion
Under, a small amount of above-mentioned hygroscopic matter is located at outside above-mentioned space and is increased the effect for absorbing moisture, so as to battery can be realized
The raising of performance, the hygroscopic matter outside above-mentioned space amount relative to the hygroscopic matter positioned at above-mentioned space
80 weight portions be 20 weight portions below in the case of, can prevent from becoming with the amount of the hygroscopic matter outside above-mentioned space
Volume excessively increase or the problem for thus reducing the energy density of per unit volume that be excessive and making active material layer.
In the electrode of lithium secondary cell of the present invention one as described above, above-mentioned active material layer may have 3 weights
Moisture rate below amount percentage, specifically, may have the moisture rate of 0.1 percentage by weight to 2 percentage by weights, more specifically
Ground, the moisture rate may with 0.5 percentage by weight to 1.5 percentage by weights.
Above-mentioned electrode of lithium secondary cell can be negative pole or positive pole, can be negative pole specifically.
The present invention provides the lithium secondary battery comprising above-mentioned electrode.
Above-mentioned lithium secondary battery can include positive pole, negative pole and the barrier film between above-mentioned positive pole and negative pole.
In the case of above-mentioned hygroscopic matter being included in active material layer, can be according to the above-mentioned hygroscopic matter for being included
Position, above-mentioned positive pole is manufactured by the manufacture method of foregoing electrode, in the case of not comprising above-mentioned hygroscopic matter,
Above-mentioned positive pole can be manufactured by known usual way in the technical field of the invention, for example, can be in positive-active
Mixed solvent in material, as needed, mixing bonding agent, conductive agent, dispersant are simultaneously stirred and prepare slurry, are inciting somebody to action afterwards
Above-mentioned slurry coating is dried after the collector of metal material and compression and manufactures positive pole.
As above-mentioned positive active material, for example, lithium and cobalt oxides (LiCoO can be enumerated2)；Lithium nickel oxide (LiNiO2)；
Li[NiaCobMncM1 d]O2(in above-mentioned formula, M1Be selected from the one kind in the group being made up of Al, Ga and In or wherein two or more
Element, 0.3≤a ＜ 1.0,0≤b≤0.5,0≤c≤0.5,0≤d≤0.1, a+b+c+d=1)；Li(LieM2 f-e-f'M3 f')
O2-gAg(in above-mentioned formula, 0≤e≤0.2,0.6≤f≤1,0≤f'≤0.2,0≤g≤0.2, M2Comprising Mn and selected from by Ni,
One or more of group of Co, Fe, Cr, V, Cu, Zn and Ti composition, M3Be selected from the group being made up of Al, Mg and B it is a kind of with
On, A is selected from one or more of group being made up of P, F, S and N) etc. lamellar compound or by a kind or more than a kind transition gold
The replaced compound of category；Li1+hMn2-hO4(in above-mentioned formula, 0≤h≤0.33), LiMnO3、LiMn2O3、LiMnO2Deng lithium manganese
Oxide；Lithium Cu oxide (Li2CuO2)；LiV3O8、V2O5、Cu2V2O7Deng barium oxide；By chemical formula LiNi1-iM4 iO2(upper
In stating formula, M4=Co, Mn, Al, Cu, Fe, Mg, B or Ga, the Ni ore deposit type lithium nickel oxides that 0.01≤y≤0.3) is represented；By chemistry
Formula LiMn2-jM5 jO2(in above-mentioned formula, M5=Co, Ni, Fe, Cr, Zn or Ta, 0.01≤y≤0.1) or by chemical formula
Li2Mn3M6O8(in above-mentioned formula, M6=Fe, Co, Ni, Cu or Zn) represent complex Li-Mn-oxide；One of the Li of chemical formula
Divide the LiMn replaced by alkaline-earth metal ions2O4；Disulfide；And LiFe3O4、Fe2(MoO4)3Deng, but be not limited thereto.
The collector of above-mentioned metal material is used as conductibility metal high, as long as it is available for the slurry of above-mentioned positive active material
Expect the metal being easily bonded, the battery will not be made to cause chemical change and the gold with high conductivity in the voltage range of battery
Category, is just not particularly limited, for example, stainless steel, aluminium, nickel, titanium, calcining carbon can be used, or uses the surface to aluminium or stainless steel
The metal being surface-treated is carried out with charcoal, nickel, titanium, silver etc..Also, fine concavo-convex improve can be formed on collector surface
The bonding force of positive active material.Collector can be with various shapes such as film, piece, paper tinsel, net, porous plastid, foaming body, non-woven body
State is used, the thickness can with 3 μm to 500 μm.
As the solvent for forming above-mentioned positive pole, there are 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), third
The organic solvents such as ketone, dimethylacetylamide or water etc., these solvents can be used alone or mix two or more and use.Solvent
Usage amount considers the applied thickness of slurry, manufacture yield, as long as above-mentioned positive active material, bonding agent, conductive agent can be made molten
Solution and scattered degree.
As above-mentioned bonding agent, it is possible to use Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP), poly- inclined fluorine
Ethene (polyvinylidenefluoride), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate
(polymethylmethacrylate), polyvinyl alcohol, carboxymethylcellulose calcium (CMC), starch, hydroxy propyl cellulose, regeneration
Cellulose, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, polyacrylic acid, ethylene propylene diene rubber (EPDM), vulcanization
Ethylene propylene diene rubber, SBR styrene butadiene rubberses (SBR), fluorubber, polyacrylic acid (poly acrylic acid) and these
Hydrogen by various bonding agent macromolecules such as Li, Na or Ca etc. substituted macromolecules or various copolymers.
As long as above-mentioned conductive agent will not make the battery cause chemical change and conductive, just it is not particularly limited, for example,
The graphite such as native graphite or Delanium can be used；Acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal black etc.
Carbon black；The conducting fibre such as carbon fiber or metallic fiber；The electric conductivity pipe such as CNT；The gold such as fluorocarbon, aluminium, nickel by powder
Category powder；The electric conductivity whisker such as zinc oxide, potassium titanate；The conductive metal oxides such as titanium oxide；Hole polypheny lene derivatives etc.
Conductive material etc..
Above-mentioned dispersant can be used the organic dispersing agents such as water class dispersant or 1-METHYLPYRROLIDONE.
Above-mentioned negative pole can in the following way be manufactured, for example, on negative electrode collector by negative electrode active material, conductive agent and
The mixture of bonding agent mixes and after preparing slurry with regulation solvent, by above-mentioned slurry coating on collector, passes through afterwards
Dry and manufacture above-mentioned negative pole.
As the negative electrode active material for being used in above-mentioned negative pole, can be usually using the carbon for being capable of occlusion and discharge lithium ion
Material, lithium metal, silicon or tin etc..Preferably, it is possible to use carbon material, and as carbon material, it is possible to use low-crystalline carbon and
High crystalline carbon etc..It is representational to have soft carbon (soft carbon) and hard carbon (hard carbon) as low-crystalline carbon, make
It is high crystalline carbon, it is representational to have native graphite, kish graphite (kish graphite), pyrolytic carbon
(pyrolyticcarbon), mesophase pitch-based carbon fibers (mesophase pitch based carbon fiber), centre
Phase carbon microspheres (meso-carbon microbeads), mesophase pitch (mesophase pitches) and oil and coal class
The high-temperature calcination carbon such as coke (petroleum or coal tar pitch derived cokes).
The thickness of above-mentioned negative electrode collector is usually 3 μm to 500 μm.As long as above-mentioned negative electrode collector will not draw the battery
Play chemical change and conductive, be just not particularly limited, for example can using copper, gold, stainless steel, aluminium, nickel, titanium, calcining carbon,
Surface to copper or stainless steel carries out metal, aluminium-cadmium alloy being surface-treated etc. with charcoal, nickel, titanium etc..Also, can also
On surface micro concavo-convex is formed to strengthen the engaging force of negative electrode active material, and can with film, piece, paper tinsel, net, porous plastid,
The variforms such as foaming body, non-woven body are used.
Above-mentioned bonding agent can maintain formed body and use to be bonded negative electrode active material particle, as long as preparing
The common bonding agent used during negative electrode active material slurry, is just not particularly limited, for example, can be used viscous as non-aqueous class
Connect polyvinyl alcohol, carboxymethylcellulose calcium, hydroxy propylene cellulose, polyacetylene fibres element, polyvinyl chloride, the polyvinylpyrrolidine of agent
Ketone, polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVdF), polyethylene or polypropylene etc., also, can be used selected from by as water
One kind in the group of the acrylonitrile-butadiene rubber of class bonding agent, SBR styrene butadiene rubberses and acrylic rubber composition or they
In mixture of more than two kinds.
Water class bonding agent is more more economical than non-aqueous class bonding agent, environmental protection, and also harmless to the health of staff, and glues
Connect that effect is more excellent than non-aqueous class bonding agent, thus the active material ratio of every same volume can be improved, so as to high power capacity can be realized
Change, as water class bonding agent, it is preferable that SBR styrene butadiene rubberses can be used.
Above-mentioned bonding agent can include below 10 percentage by weights in the overall weight of negative electrode active material slurry, specifically
Ground, can include 0.1 percentage by weight to 10 percentage by weights.If the content of above-mentioned bonding agent is less than 0.1 percentage by weight, lead to
Cross having little effect of being produced using bonding agent and not preferably, if the content of above-mentioned bonding agent is more than 10 percentage by weights,
Because the content of bonding agent increase the relative amount of active material is reduced so that in the presence of every volume capacity decline hidden danger and simultaneously
It is not preferred.
As long as above-mentioned conductive agent will not make the battery cause chemical change and conductive, just it is not particularly limited, for example,
The graphite such as native graphite or Delanium can be used；Acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal black
Deng carbon black；The conducting fibre such as carbon fiber or metallic fiber；The metal dusts such as fluorocarbons, aluminium, nickel by powder；Zinc oxide, potassium titanate
Etc. electric conductivity whisker；The conductive metal oxides such as titanium oxide；And the conductive material such as polypheny lene derivatives etc..It is above-mentioned to lead
It is amount of 1 percentage by weight to 9 percentage by weights that electric agent can be used relative to the overall weight of negative electrode active material slurry.
As the solvent for forming above-mentioned negative pole, with 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF),
The organic solvents such as acetone, dimethylacetylamide or water etc., these solvents can be used alone or mix two or more and use.It is molten
The usage amount of agent considers the applied thickness of slurry, yield is prepared, as long as above-mentioned negative electrode active material, bonding agent, conduction can be made
Agent is dissolved and scattered degree.
As needed, above-mentioned negative pole can also include the thickener for adjusting viscosity.
Above-mentioned thickener can be cellulose compound, for example, can be selected from by carboxymethylcellulose calcium (CMC), hydroxyl
More than a kind of material in the group of methylcellulose, hydroxyethyl cellulose and hydroxypropyl cellulose composition, specifically, Ke Yiwei
, can with thickener together be dispersed in water for above-mentioned negative electrode active material and bonding agent to be applied to by carboxymethylcellulose calcium (CMC)
Negative pole.
On the other hand, as barrier film, the common porous polymer membrane as barrier film in the past can be used, for example, can be by
Alathon, Noblen, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymerization
Thing etc. is used alone by the porous polymer membrane that polyolefin macromolecular is manufactured or is laminated them and uses, or can be used
Common porous nonwoven cloth, for example, can be used by shapes such as dystectic glass fibre, pet fibers
Into non-woven fabrics, but be not limited thereto.
The lithium salts that can be included as the electrolyte for being used in the present invention can unrestrictedly be used and is typically used in
The material of secondary lithium batteries electrolyte, for example, can be selected from by F as the anion of above-mentioned lithium salts-、Cl-、Br-、I-、
NO3 -、N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、
CF3SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、
(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-And (CF3CF2SO2)2N-A kind of material in the group of composition.
As electrolyte of the invention is used in, the organic liquid that can be used when lithium secondary battery is manufactured can be enumerated
Body electrolyte, inorganic liquid electrolyte, solid macromolecule electrolyte, gluey polyelectrolyte, solid inorganic electrolytes and
Fusion inorganic electrolyte etc., but be not limited thereto.
The profile of lithium secondary battery of the invention is not particularly limited, and can be in use cylindrical shape, the square, bag of tank
(pouch) shape or coin (coin) shape.
Lithium secondary battery of the invention can not only be used in the secondary battery unit of the power supply as midget plant, Er Qieyou
Selection of land, it is also possible to be used in the unit cells of the medium-and-large-sized battery model including multiple secondary battery units.
The preference of above-mentioned medium-and-large-sized device can enumerate electric automobile, mixed power electric car, plug-in mixing move
Power electric automobile and accumulating system etc., but be not limited to that this.
Embodiment
Hereinafter, embodiment and experimental example are enumerated and is illustrated in more detail to illustrate the present invention, but this hair
It is bright to be not limited to these embodiments and experimental example.Embodiments of the invention can be changed to variform, shall not be construed as this
The scope of invention is confined to following embodiments.Embodiments of the invention are in order to the common skill of the technical field of the invention
What art personnel were described more fully the present invention and provided.
Embodiment 1：The manufacture of the negative electrode for lithium secondary battery comprising hygroscopic matter
It is graphite, the second of 1 percentage by weight of 25 μm of 86 percentage by weights to average grain diameter as negative electrode active material
The CMC (thickener) of acetylene black (Denka black) (conductive agent), the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight
Mixed to have prepared cathode size with as the NMP of solvent.By the above-mentioned negative electrode active material slurry prepared with 65 μ
The thickness of m is coated on and forms active material layer as 10 μm of one sides of the copper of negative electrode collector (Cu) film, and it is carried out
Drying, afterwards to the average grain diameter (D as hygroscopic matter50) it is 0.5 μm of silica gel with 1/10 weight as above-mentioned graphite
The mode for measuring the amount of part is mixed with NMP and has been prepared mixed liquor, above-mentioned mixed liquor is slowly permeated in above-mentioned active matter
Matter layer 30 minutes.If completing the infiltration of mixed liquor, it is dried and is rolled, made so that prescribed level is punched out afterwards
Negative pole is made.
Embodiment 2 is to embodiment 5
In addition to the particle diameter of above-mentioned silica gel is changed into particle diameter as shown in table 1 below, with the identical of above-described embodiment 1
Method has manufactured negative pole.
Embodiment 6 is to embodiment 10
Except using size as shown in table 1 below and/or diverse hygroscopic matter to replace as hygroscopic matter
Above-mentioned average grain diameter (D50) it is outside 0.5 μm of silica gel, negative pole have been manufactured with the identical method of above-described embodiment 1.
Embodiment 11
It is 25 μm of graphite and the average grain diameter of 1 weight portion as hygroscopic matter to the average grain diameter of 100 weight portions
(D50) it is that 0.5 μm of silica gel carries out the dry-mixing of 30 minutes with the mixing speed of 25rpm, so as to manufacture on surface is glued with
State the graphite of silica gel.
As negative electrode active material, graphite, 1 weight percent of above-mentioned silica gel are glued with surface to 86 percentage by weights
The CMC (thickener) of the acetylene black (conductive agent) of ratio, the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as molten
The NMP of agent is mixed to have prepared cathode size.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
It is coated on and forms active material layer as the one side of copper (Cu) film of 10 μm of negative electrode collector, and it is done
It is dry, afterwards to the average grain diameter (D as hygroscopic matter50) it is 0.5 μm of silica gel with 9/100 weight portion as above-mentioned graphite
The mode of amount mixed to have prepared mixed liquor with NMP, above-mentioned mixed liquor is slowly permeated in above-mentioned active material layer
30 minutes.If completing the infiltration of mixed liquor, it is dried and is rolled, manufactured so that prescribed level is punched out afterwards
Negative pole.
Embodiment 12
Except being used by average grain diameter (D in above-described embodiment 1150) it is 2 μm of silica gel and average grain diameter (D50) be
The P of 100nm2O5With 80:20 weight replaces as the above-mentioned average grain diameter of hygroscopic matter than the mixture for mixing
(D50) it is outside 0.5 μm of silica gel, negative pole have been manufactured with the identical method of above-described embodiment 11.
Embodiment 13
The average grain of 3 weight portions to graphite that the average grain diameter by 100 weight portions is 25 μm and as hygroscopic matter
Footpath (D50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5With 80:20 weight than the mixture that mixes with
The speed of 25rpm carries out the dry-mixing of 30 minutes, has thus manufactured and has been glued with above-mentioned silica gel and P on surface2O5Graphite.
Used as negative electrode active material, the surface to 86 percentage by weights is glued with above-mentioned silica gel and P2O5Graphite, 1 weight
The CMC (thickener) of the acetylene black (conductive agent) of percentage, the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight and work
Mixed to have prepared cathode size for the NMP of solvent.By the above-mentioned negative electrode active material slurry prepared with 65 μm
Thickness is coated on and forms active material layer as the one side of copper (Cu) film of 10 μm of negative electrode collector, and is done
It is dry, afterwards to by the average grain diameter (D as hygroscopic matter50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5
With 80:20 weight is carried out in the way of the amount of 7/100 weight portion as above-mentioned graphite than the mixture for mixing with NMP
Mixed liquor has been prepared in mixing, above-mentioned mixed liquor is slowly permeated in above-mentioned active material layer 30 minutes.If completing mixed liquor
Infiltration, then it is dried and is rolled, negative pole has been manufactured so that prescribed level is punched out afterwards.
Embodiment 14
Particle diameter to 80 weight portions is 0.5 μm of silica gel, the acetylene black (conductive agent) of 1 weight portion and the SBR of 2 weight portions
(bonding agent) is mixed to have prepared mixture with as the NMP of solvent, is applied with 2 μm of thickness by said mixture
Dried after as 10 μm of one sides of the copper of negative electrode collector (Cu) film.Now, above-mentioned silica gel use relative to
As the amount that the above-mentioned graphite of negative electrode active material is 1/100 weight portion.
It is 25 μm of graphite, the second of 1 percentage by weight to the average grain diameter of 86 percentage by weights as negative electrode active material
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as solvent
NMP is mixed to have prepared cathode size.The above-mentioned negative electrode active material slurry prepared is applied with 65 μm of thickness
Active material layer is formed in the Copper thin film for being coated with said mixture, and it is dried, afterwards as hygroscopicity thing
Matter, is that 0.5 μm of silica gel is mixed to make in the way of the amount of 9/100 weight portion as above-mentioned graphite with NMP to particle diameter
It is standby gone out mixed liquor, above-mentioned mixed liquor is slowly permeated in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor,
It is dried and is rolled, manufactured negative pole so that prescribed level is punched out afterwards.
Embodiment 15
Except being used by average grain diameter (D in above-described embodiment 1450) it is 2 μm of silica gel and average grain diameter (D50) be
The P of 100nm2O5With 80:20 weight replaces as the above-mentioned average grain diameter of hygroscopic matter than the mixture for mixing
(D50) it is outside 0.5 μm of silica gel, negative pole have been manufactured with the identical method of above-described embodiment 14.
Embodiment 16
To the average grain diameter (D by 80 weight portions50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5With 80:
20 weight is than the mixture, the acetylene black (conductive agent) of 1 weight portion, the SBR (bonding agent) of 2 weight portions and the conduct that mix
The NMP of solvent is mixed to have prepared mixture, is coated on as 10 μm of negative poles using 2 μm of thickness by said mixture
The one side of copper (Cu) film of collector, is dried to it afterwards.Now, said mixture has been used relative to as negative
The above-mentioned graphite of pole active material is the amount of 1/10 weight portion.
It is 25 μm of graphite, the second of 1 percentage by weight to the average grain diameter of 86 percentage by weights as negative electrode active material
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as solvent
NMP is mixed to have prepared cathode size.The above-mentioned negative electrode active material slurry prepared is applied with 65 μm of thickness
Active material layer is formed in the Copper thin film for being coated with said mixture, and it is dried, afterwards to by as moisture absorption
Average grain diameter (the D of property material50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5With 80:20 weight is than mixing
Mixture mixed to have prepared mixing with NMP in the way of the amount of 9/100 weight portion as above-mentioned graphite
Liquid, makes above-mentioned mixed liquor slowly permeate in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor, it is done
It is dry and roll, negative pole has been manufactured so that prescribed level is punched out afterwards.
Embodiment 17
It is that 25 μm of graphite and silica gel that the particle diameter of 0.5 weight portion is 0.5 μm are done to the average grain diameter of 100 weight portions
Mixing and hard mixing, and manufactured and be glued with the graphite of above-mentioned silica gel on surface.
Particle diameter to 80 weight portions is 0.5 μm of silica gel, the acetylene black (conductive agent) of 1 weight portion and the SBR of 2 weight portions
(bonding agent) is mixed to have prepared mixture with as the NMP of solvent, and said mixture is coated on 2 μm of thickness
As being dried to it after 10 μm of one sides of the Copper thin film of negative electrode collector.Now, above-mentioned silica gel used relative to
As the amount that the above-mentioned graphite of negative electrode active material is 1/200 weight portion.
As negative electrode active material, graphite, 1 weight percent of above-mentioned silica gel are glued with surface to 86 percentage by weights
The CMC (thickener) of the acetylene black (conductive agent) of ratio, the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as molten
The NMP of agent is mixed to have prepared cathode size.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
It is coated on the Copper thin film that is coated with said mixture and forms active material layer, and it is dried, afterwards as moisture absorption
Property material, is that 0.5 μm of silica gel is mixed in the way of the amount of 9/100 weight portion as above-mentioned graphite with NMP to particle diameter
To prepare mixed liquor, above-mentioned mixed liquor is set slowly to permeate in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor,
Then it is dried and is rolled, manufactured negative pole so that prescribed level is punched out afterwards.
Embodiment 18
It is different with size as shown in table 1 below and/or species except being used as hygroscopic matter in above-described embodiment 17
Hygroscopic matter, come instead of outside silica gel that above-mentioned particle diameter is 0.5 μm, being prepared with the identical method of above-described embodiment 17
Negative pole.
Embodiment 19
To graphite and the average grain diameter (D of 2 weight portions that the average grain diameter by 100 weight portions is 25 μm50) it is 2 μm of silica gel
With average grain diameter (D50) it is the P of 100nm2O5With 80:20 weight come the mixture that mixes than having carried out dry-mixing and hard
Mixing, has thus manufactured and has been glued with above-mentioned silica gel and P on surface2O5Mixture graphite.
To the average grain diameter (D by 80 weight portions50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5With 80:
The SBR (bonding agent) and work of mixture, the acetylene black (conductive agent) of 1 weight portion and 2 weight portions of 20 weight than mixing
Mixed to prepare mixture for the NMP of solvent, said mixture is coated on as 10 μm of negative pole collection using 2 μm of thickness
It is dried after the one side of copper (Cu) film of electric body.Now, above-mentioned silica gel has been used and lived relative to as negative pole
The graphite of property material is the amount of 2/100 weight portion.
As negative electrode active material, above-mentioned silica gel and P are glued with surface to 86 percentage by weights2O5Mixture
Graphite, the acetylene black (conductive agent) of 1 percentage by weight, the SBR (bonding agent) and the CMC of 1 percentage by weight of 2 percentage by weights
(thickener) is mixed to have prepared cathode size with as the NMP of solvent.By the above-mentioned negative electrode active material prepared
Slurry is coated on 65 μm of thickness and is coated with the Copper thin film of said mixture and forms active material layer, and it is done
It is dry, afterwards as hygroscopic matter, to by average grain diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 100nm2O5
With 80:20 weight is carried out in the way of the amount of 6/100 weight portion as above-mentioned graphite than the mixture for mixing with NMP
Mixed liquor has been prepared in mixing, above-mentioned mixed liquor is slowly permeated in above-mentioned active material layer 30 minutes.If completing mixed liquor
Infiltration, then it is dried and is rolled, negative pole has been manufactured so that prescribed level is punched out afterwards.
Embodiment 20
It is 25 μm of graphite, the second of 1 percentage by weight to the average grain diameter of 86 percentage by weights as negative electrode active material
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as solvent
NMP is mixed to prepare cathode size.The above-mentioned negative electrode active material slurry prepared is coated on 65 μm of thickness
Form active material layer and it is dried as the one side of copper (Cu) film of 10 μm of negative electrode collector, Zhi Houzuo
It is hygroscopic matter, to by average grain diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) it is the P of 5nm2O5With 80:20 weight
Measure and mixed to prepare with NMP in the way of the amount of 9/100 weight portion as above-mentioned graphite than the mixture for mixing
Go out mixed liquor, above-mentioned mixed liquor is slowly permeated in above-mentioned active material layer 30 minutes.If the infiltration of mixed liquor is completed, to it
It is dried and rolls, has manufactured negative pole so that prescribed level is punched out afterwards.
Comparative example 1
It is that 25 μm of graphite and silica gel that the particle diameter of 10 weight portions is 0.5 μm are done to the average grain diameter of 100 weight portions
Mixing and hard mixing, and manufactured and be glued with the graphite of above-mentioned silica gel on surface.
As negative electrode active material, graphite, 1 weight percent of 86 percentage by weights to being glued with above-mentioned silica gel on surface
The CMC (thickener) of the acetylene black (conductive agent) of ratio, the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as molten
The NMP of agent is mixed to have prepared cathode size.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
It is coated on and forms active material layer as 10 μm of one sides of the copper of negative electrode collector (Cu) film, and it is dried and pressed
Prolong, manufactured negative pole so that prescribed level is punched out afterwards.
Comparative example 2
Particle diameter to 80 weight portions is 0.5 μm of silica gel, the acetylene black (conductive agent) of 1 weight portion and the SBR of 2 weight portions
(bonding agent) is mixed to prepare mixture with as the NMP of solvent, and said mixture is coated on into work with 2 μm of thickness
To be dried after 10 μm of one sides of the copper of negative electrode collector (Cu) film.
It is 25 μm of graphite, the second of 1 percentage by weight to the average grain diameter of 86 percentage by weights as negative electrode active material
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 percentage by weights and 1 percentage by weight with as solvent
NMP is mixed to prepare cathode size.The above-mentioned negative electrode active material slurry prepared is coated on 65 μm of thickness
It is coated with the Copper thin film of said mixture and forms active material layer, and it is dried and rolled, afterwards with prescribed level
It is punched out and has manufactured negative pole.
Table 1
Embodiment 1-1 to embodiment 20-1：The manufacture of the lithium secondary battery comprising hygroscopic matter
Manufactured in respectively from above-described embodiment 1 to embodiment 20 in the perforated membrane of the polyethylene agent for making thickness be 17 μm
Negative pole and lithium metal between after, by ethylene carbonate (EC) and diethyl carbonate (DEC) with 30:70 volume ratio mixing
Solution in injection be dissolved with the LiPF of 1M6Electrolyte and manufactured coin-like half cells respectively.
Comparative example 1-1 to comparative example 2-1：The manufacture of the lithium secondary battery comprising hygroscopic matter
Manufactured in respectively from above-mentioned comparative example 1 to comparative example 2 in the perforated membrane of the polyethylene agent for making thickness be 17 μm
Negative pole and lithium metal between after, by ethylene carbonate (EC) and diethyl carbonate (DEC) with 30:70 volume ratio mixing
Solution in injection be dissolved with the LiPF of 1M6Electrolyte and manufactured coin-like half cells respectively.
Experimental example 1：Cycle characteristics evaluation experimental
In order to the Coin shape for obtaining respectively from embodiment 1-1 to embodiment 20-1, in comparative example 1-1 and comparative example 2-1
Half-cell confirms cycle characteristics, and electrochemical evaluation experiment is implemented as follows.
Specifically, the coin to obtaining respectively from embodiment 1-1 to embodiment 20-1, in comparative example 1-1 and comparative example 2-1
Type half-cell is charged at 25 DEG C with the constant current (CC) of 0.5C, until its voltage reaches 0.005V, afterwards by perseverance
Determining voltage (CV) carries out 1 charging, until charging current reaches 0.005C (cut-off current：Cut-off current).Exist afterwards
Placement is charged for 20 minutes by the constant current (CC) of 0.5C afterwards, until its voltage reaches 1.5V.By above-mentioned steps with
The mode of circulation is implemented 1 to 100 time repeatedly.Figure 4 illustrates the capacity maintenance after being circulated by 100 times to battery
The measurement result that rate is measured.
Reference picture 4, it is known that, the hygroscopic matter big relative to particle diameter, particle diameter small hygroscopic matter is followed by 100 times
Capacity sustainment rate after ring is more preferable.Specifically, the result of embodiment 1-1 to embodiment 4-1 is observed, it is known that, if hygroscopicity thing
The particle diameter of matter is small, then improved cycle performance.But, as confirmed from embodiment 5-1, can confirm that, in moisture absorption
Property material particle diameter it is excessively small in the case of, make the consumption of electrolyte big because of the side reaction of the electrolyte in surface so that
Cycle performance produces bad influence on the contrary.
On the other hand, can also confirm that, according to the position of hygroscopic matter, the capacity dimension after being circulated by 100 times
Holdup changes.Specifically, if being compared to the result of embodiment 1-1, comparative example 1-1 and 2-1, can confirm that, i.e.,
Make the species of hygroscopic matter identical, also according to its position, the capacity sustainment rate after being circulated by 100 times has differences, especially
Its, in the case where hygroscopic matter is located at space, relative to hygroscopic matter be located at active material surface or active material with
Situation between collector, capacity sustainment rate is more excellent, and is located between active material and collector relative to hygroscopic matter
Situation, in the case of positioned at active material surface, capacity sustainment rate is relatively excellent.
On the other hand, it is known that, mixed with 2 kinds of hygroscopic matters of distinct by 2 kinds of hygroscopic matters of different sizes
In the case of closing use, compared with unmixed situation about using, the capacity sustainment rate after being circulated by 100 times is higher.
Claims (19)
1. a kind of electrode of lithium secondary cell, comprising active material layer and collector,
The electrode of lithium secondary cell is characterised by,
The active material layer includes active material and hygroscopic matter,
Between the hygroscopic matter is located at the space for being arranged and being formed by the active material in the active material layer.
2. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter is selected from by silica gel, zeolite, CaO, BaO, MgSO4、Mg(ClO4)2、MgO、P2O5、Al2O3、CaH2、
NaH、LiAlH4、CaSO4、Na2SO4、CaCO3、K2CO3、CaCl2, 4A molecular sieves and 3A molecular sieves, Ba (ClO4)2, crosslinking combine
Polyacrylic acid and polyacrylic acid composition one or more of group material.
3. electrode of lithium secondary cell according to claim 1, it is characterised in that
Average grain diameter (the D of the active material50) it is 0.1 to 30 μm.
4. electrode of lithium secondary cell according to claim 1, it is characterised in that
The size in the space is 0.01 to 20 μm.
5. electrode of lithium secondary cell according to claim 1, it is characterised in that
Average grain diameter (the D of the hygroscopic matter50) size be average grain diameter (D relative to the active material50)
0.1% to 70%.
6. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter includes 1 to 20 weight portion on the basis of the active material of 100 weight portions.
7. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter is with 1 μm to 20 μm average grain diameter (D50) the first hygroscopic matter and with 10nm to 1 μm
Average grain diameter (D50) the second hygroscopic matter mixture.
8. electrode of lithium secondary cell according to claim 7, it is characterised in that
First hygroscopic matter and second hygroscopic matter are with 60:40 to 99:1 weight ratio is mixed.
9. electrode of lithium secondary cell according to claim 7, it is characterised in that
First hygroscopic matter is selected from the polyacrylic acid combined by silica gel, zeolite, 4A molecular sieves and 3A molecular sieves, crosslinking
And the material of one or more of the group of polyacrylic acid composition,
Second hygroscopic matter is selected from by CaO, BaO, MgSO4、Mg(ClO4)2、MgO、P2O5、Al2O3、CaH2、NaH、
LiAlH4、CaSO4、Na2SO4、CaCO3、K2CO3And Ba (ClO4)2The material of one or more of the group of composition.
10. electrode of lithium secondary cell according to claim 1, it is characterised in that
The voidage of the active material layer is 10% to 40%.
11. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter is also additionally located at the surface of the active material in addition to positioned at the space,
Hygroscopic matter and the weight ratio of the hygroscopic matter positioned at the active material surface positioned at the space are 99.9:
0.1 to 80:20.
12. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter is also additionally located between the active material layer and collector in addition to positioned at the space,
Positioned at the hygroscopic matter and the weight of the hygroscopic matter between the active material layer and collector in the space
Amount is than being 99.9:0.1 to 80:20.
13. electrode of lithium secondary cell according to claim 1, it is characterised in that
The hygroscopic matter is in addition to positioned at the space also additionally positioned at the surface of the active material and the work
Property is between material layer and collector,
The hygroscopicity thing between the space, the surface of the active material and the active material layer and collector is located at respectively
The weight ratio of matter is 99.9:0.05:0.05 to 80:10:10.
14. electrode of lithium secondary cell according to claim 1, it is characterised in that
The moisture rate of the active material layer is below 3 percentage by weights.
15. a kind of lithium secondary batteries, comprising the electrode of lithium secondary cell any one of claim 1 to 14.
A kind of 16. manufacture methods of electrode of lithium secondary cell, including：
Step (1), applies active material layer is formed containing the slurry of active material on the current collector；And
Step (2), the dispersion liquid containing hygroscopic matter is permeated in the active material layer, so that the hygroscopic matter
Between the space for being arranged and being formed by the active material.
The manufacture method of 17. electrode of lithium secondary cell according to claim 16, it is characterised in that
Before the step (1), additionally including carrying out dry-mixing or hard mixing to the active material and hygroscopic matter
And the step of the hygroscopic matter is close to the active material surface.
The manufacture method of 18. electrode of lithium secondary cell according to claim 16, it is characterised in that
Before the step (1), additionally including coating on the collector is mixed in hygroscopic matter and bonding agent
The step of mixture of solvent.
The manufacture method of 19. electrode of lithium secondary cell according to claim 18, it is characterised in that
Before the step (2), additionally including coating on the collector is mixed in hygroscopic matter and bonding agent
The step of mixture of solvent.
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| KR10-2015-0158422 | 2015-11-11 | ||
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| KR1020160143357A KR102088858B1 (en) | 2015-11-11 | 2016-10-31 | Electrode for lithium secondary battery comprising hygroscopic materials and lithium secondary battery comprising the same |
| KR10-2016-0143357 | 2016-10-31 |
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| KR20170055419A (en) | 2017-05-19 |
| CN106848379B (en) | 2019-07-26 |
| KR102088858B1 (en) | 2020-03-13 |
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Effective date of registration: 20211209 Address after: Seoul, South Kerean Patentee after: LG Energy Solution,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |