CN106848379B - 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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- CN106848379B CN106848379B CN201610997975.5A CN201610997975A CN106848379B CN 106848379 B CN106848379 B CN 106848379B CN 201610997975 A CN201610997975 A CN 201610997975A CN 106848379 B CN106848379 B CN 106848379B
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- H01M10/052—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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to the electrode of lithium secondary cell containing hygroscopic matter and include its lithium secondary battery, it is related to hygroscopic matter and is being located at the electrode of lithium secondary cell arranged by above-mentioned active material and between the gap that is formed in active material layer, in electrode of lithium secondary cell of the invention, hygroscopic matter is being located between the gap formed by active material in active material layer, the moisture for being present in electrode and electrolyte can thus be removed, so as to exclude the side reaction because caused by battery there are moisture, 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 comprising its lithium secondary battery, in more detail
Ground is related to comprising that can improve the secondary lithium batteries of battery performance for removing the hygroscopic materials of the fine moisture of electrode
Electrode and lithium secondary battery comprising it.
Background technique
With the 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 adds.In this secondary battery, it shows 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 improves, to can substitute as the master for causing atmosphere pollution
Want gasoline vehicle, diesel vehicle of one of reason etc. using the vehicle of fossil fuel, such as to electric car (EV), hybrid power electricity
The research of electrical automobile (HEV) carries out more.As the dynamic of this electric car (EV), mixed power electric car (HEV) etc.
Power source mainly uses ni-mh metal (Ni-MH) secondary cell, but to using with high-energy density, high discharge voltage and output
Research in terms of the lithium secondary battery of stability just actively carries out, and a part of commercialization.
Lithium secondary battery is formed by wrapping the structure that nonaqueous electrolytic containing lithium salt is impregnated in electrode assembly, in above-mentioned electrode
In component, porosity seperation film is between the anode (positive for being coated with active material on electrode collector respectively
Electrode) between cathode (negative electrode).
In the case where moisture is contained in the inside of this lithium secondary battery, this is likely to become the reason of 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 existing
Form is contained in electrolyte.For example, the Li-Ti oxide as negative electrode active material is during charging and discharging because structure becomes
Change extremely low zero deformation rate (zero-strain) substance and life characteristic is very excellent, and forms relatively high voltage section, and
Ingotism (dendrite) is not generated, thus it is very excellent as safety (safety) and stability (stability)
Substance it is well-known, also, have the advantages that the used in rapid charging pole characteristic that can be charged in moisture, but because
Property due to absorbing moisture in air exists because contained by using above-mentioned Li-Ti oxide to manufacture electrode
Moisture be decomposed and lead to the problem of bulk gas.
Also, existing moisture occurs anti-by the electrical potential energy provided during the charging process and with electrolyte in the electrolytic solution
It answers, it is possible to the phenomenon that generating gas and causing cell expansion etc., may be decreased the reliability of battery.For example, electrolyte
The LiPF for being included6Lithium salts and water react and form the HF as strong acid, are formed by HF active and show alkalescent
Electrode active material react and dissolve out electrode active material ingredient, as a result, leading to the degeneration of battery, and just
Pole surface forms the resistance in lithium fluoride (LiF) Lai Zengjia electrode, and generates gas, declines so as to cause the service life of battery.
A variety of methods are utilized in order to remove the moisture inside lithium secondary battery as a result, for example, in order to remove the secondary electricity of lithium
The moisture of the electrode in pond removes the moisture of electrode by high temperature drying process, also, sharp in order to remove the moisture of electrolyte
Used in the method (Korean Patent Publication No. 2015-0037332) etc. of the configuration hygroscopic material such as battery case.
But only can not be by the moisture removal of electrode to desired degree by the above method, thus need to develop one
Kind can improve the new technology of battery performance and more effectively removing the moisture of electrode.
Summary of the invention
Project to be solved by this invention is, provides due to being effectively removed and being possibly comprised in containing hygroscopic matter
The moisture of the electrode of lithium secondary battery and electrolyte is so as to improving the electrode of lithium secondary cell of battery performance.
Another project to be solved by this invention is, provides secondary lithium batteries as described above containing hygroscopic matter
The manufacturing method of electrode.
According to an embodiment, the present invention provides following electrode of lithium secondary cell, that is, electrode of lithium secondary cell includes
Active material layer and collector, above-mentioned active material layer include active material and hygroscopic matter, and above-mentioned hygroscopic matter is upper
It states between the gap for being located in active material layer and being formed by above-mentioned active material.
According to another embodiment, the present invention provides the manufacturing method of following electrode of lithium secondary cell, that is, the secondary electricity of lithium
The manufacturing method of pond electrode includes: step (1), applies the slurry containing active material on the current collector and forms active material
Layer；And step (2), the dispersion liquid containing hygroscopic matter is permeated in above-mentioned active material layer, to make above-mentioned hygroscopicity
Substance is located at by between above-mentioned active material arranges and is formed gap.
In active material layer, hygroscopic matter is located to be formed by active material for electrode of lithium secondary cell of the invention
Between gap, it is thus possible to removal moisture present in electrode and electrolyte, so as to exclude because there are water in battery
Side reaction caused by point, thus, it is possible to improve battery performance.
Detailed description of the invention
Fig. 1 is to be schematically illustrated in hygroscopic matter in active material layer to be located at the gap for being arranged by active material and being formed
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 form of the hygroscopic matter between active material and collector.
Fig. 4 is to indicate in the battery and comparative example 1-1 to comparative example 3-1 for making embodiment 1-1 to embodiment 19-1 respectively
Battery by 100 times circulation after the measurement result that the capacity maintenance rate of battery is measured chart.
Specific embodiment
Hereinafter, the present invention is described in more detail in order to help to understand the present invention.
The term used in this specification and the claimed range of invention should not be with the meaning in routine or dictionary
Limit and explain, but to illustrate its invention based on inventor in optimal method and can be suitable to the concept of term
Principle that locality is defined is explained with meaning and concept of the technical idea of the present invention.
Electrode of lithium secondary cell of the invention includes active material layer and collector, and above-mentioned active material layer includes activity
Substance and hygroscopic matter, above-mentioned hygroscopic matter is located in above-mentioned active material layer to be arranged by above-mentioned active material and is formed
Gap between.
Above-mentioned hygroscopic matter is executable to including moisture, such as moisture of electrode and the moisture of electrolyte in battery
Etc. the function of being absorbed and removed, due to being located at by between above-mentioned active material arranges and is formed gap, because without producing
The problem of raw energy density for making the overall volume of active material layer become larger and making per unit volume reduces.
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 sieve and 3A molecular sieve, Ba
(ClO4)2, one or more of the group of poly- (acrylic acid) and poly- (acrylic acid) composition that combines of crosslinking, specifically, can for 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, can have 1 μm to 5 μm of average grain diameter.
When above-mentioned active material has 0.1 μm to 30 μm of average grain diameter (D50) when, it is arranged and shape by above-mentioned active material
At gap 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.At this point, when assuming that there is ball with its inscribe in above-mentioned gap, above-mentioned gap it is big
It is small to be indicated by the partial size of above-mentioned ball.
Above-mentioned hygroscopic matter can be can include by the mode in above-mentioned active material arranges and is formed gap
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 object
Average grain diameter (D of the matter relative to above-mentioned active material50) can have 0.1% to 70% average grain diameter (D50) size, specifically
Ground can have 1% to 67% average grain diameter (D50) size, more specifically, can have 5% to 50% average grain diameter (D50)
Size.
It is big with 0.1% or more average grain diameter relative to the average grain diameter of above-mentioned active material in above-mentioned hygroscopic matter
In the case where small, fill while above-mentioned hygroscopic matter tight can be prevented arranged by above-mentioned active material and the gap that is formed from
And the problem of blocking the channel that electrolyte can impregnate, in average grain diameter of the above-mentioned hygroscopic matter relative to above-mentioned active material
In the case where with 70% Average Particle Diameters below, can prevent following problem: above-mentioned hygroscopic matter becomes than above-mentioned
The size in gap is big and is located at the part outside gap, or interferes 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) partial size 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 measures.Above-mentioned laser diffractometry can usually be measured from the sub-micron field (submicron) to several mm
The partial size of degree, the available result with high reproducibility and high de-agglomeration.
On the basis of the above-mentioned active material of 100 parts by weight, above-mentioned hygroscopic matter may include 1 parts by weight to 20 weight
Part, it is preferable that it may include 2 parts by weight to 10 parts by weight, it is highly preferred that may include 3 parts by weight to 7 parts by weight.
If the content of above-mentioned hygroscopic matter is 1 parts by weight or more on the basis of the above-mentioned active material of 100 parts by weight,
Moisture absorption appropriate can be showed, if 20 parts by weight hereinafter, can then prevent following problem: the gap of above-mentioned active material layer
It can excessively reduce or above-mentioned hygroscopic matter interferes contact between above-mentioned active material, or make the whole body of active material layer
Product increases and reduces the energy density of per unit density.
Above-mentioned hygroscopic matter can be the mixing mixed by the 2 kinds of hygroscopic matters classified according to particle size
Object, specifically, the mixture of above-mentioned hygroscopic matter can be relatively small for size relatively large the first hygroscopic matter and size
The second hygroscopic matter mixture.
In this way, mixed comprising the second relatively small hygroscopic matter of the first relatively large hygroscopic matter of size and size
In the case where closing object, above-mentioned hygroscopic matter can more efficiently in the gap between above-mentioned active material, so as to
Inhibit the energy that the overall volume increase of active material layer thus per unit density due to comprising above-mentioned hygroscopic matter occurs close
The phenomenon that degree reduces.
Above-mentioned first hygroscopic matter can have 1 μm to 20 μm of average grain diameter (D50), specifically, can have 5 μm to 20 μ
Average grain diameter (the D of m50), more specifically, can have 5 μm to 10 μm of average grain diameter (D50), 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)。
At this point, the first hygroscopic matter and the second hygroscopic matter can be mixed with the weight ratio of 60:40 to 99:1, have
Body can mix with the weight ratio of 70:30 to 98:2, more specifically, can be mixed with the weight ratio of 80:20 to 95:5
It closes.
In the case where the weight ratio of the first hygroscopic matter and the second hygroscopic matter is met the above range, can inhibit
The volume of active material layer increases, and is uniformly dispersed hygroscopic matter, and further increases moisture absorption, can prevent moisture absorption
Property substance interfere electrolyte permeability.
The specific type of above-mentioned first hygroscopic matter and the second hygroscopic matter can be identical or different, but can lead to
It crosses the type for being appropriately combined the first hygroscopic matter and the second hygroscopic matter and moisture absorption is made more to maximize.
In an example of the invention, above-mentioned first hygroscopic matter can be for selected from by silica gel, zeolite, 4A molecular sieve and 3A
One or more of the group of poly- (acrylic acid) and poly- (acrylic acid) composition that molecular sieve, crosslinking combine, above-mentioned second hygroscopicity
Substance can be for 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
For selected from by silica gel, zeolite, BaO and MgSO4One or more of group of composition, above-mentioned second hygroscopic matter can for selected from
By MgO, P2O5And Al2O3One or more of group of composition.
The active material layer of above-mentioned electrode of lithium secondary cell may include active material and hygroscopic matter, and have
10% to 40% voidage specifically can have 20% to 30% voidage, more specifically, can have 25% to 30%
Voidage.
In the case where the voidage of active material layer is met the above range, electrolyte can be made suitably to permeate, can get
More excellent moisture absorption.
It is located at above-mentioned hygroscopic matter not limited especially by the method between above-mentioned active material arranges and is formed gap
It is fixed, for example, can realize by the following method, that is, the above method includes: step (1), and coating contains active matter on the current collector
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 it is located at above-mentioned hygroscopic matter by between above-mentioned active material arranges and is formed gap.
At this point, above-mentioned slurry can according to need to be contained in above-mentioned active material layer active material add bonding agent,
Conductive agent and mixed with solvent to prepare.Above-mentioned active material layer, which can be additionally carried out, makes above-mentioned dispersion liquid permeate it
The step compressed and dried afterwards can carry out the step that above-mentioned active material layer is preferentially dried before above-mentioned dispersion liquid permeates
Suddenly.By method as described above, can make above-mentioned hygroscopic matter be located at arranged by above-mentioned active material and the gap that is formed it
Between, it is illustrated schematically in Fig. 1.
As needed, above-mentioned hygroscopic matter can also be located at except above-mentioned gap, for example, can 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 where being located at above-mentioned hygroscopic matter except gap, hygroscopic matter is eventually made also to be configured at the activity of above-mentioned electrode
Except the gap of material layer, thus the presence of the hygroscopic matter of more uniform dispersion can play and effectively absorb electric pool inner water
The effect divided, but the overall volume that the presence for being located at the hygroscopic matter except above-mentioned gap may cause active material layer increases
Greatly, thus need suitably to adjust 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 in Fig. 3 and is located at above-mentioned active material and collection
Form between electric body.
It is located at above-mentioned hygroscopic matter by between above-mentioned active material arranges and is formed gap and above-mentioned active material
The method on surface is not particularly limited, for example, can realize by the following method, that is, 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 arranged by above-mentioned active material and the gap that is formed it
Between, it additionally include that dry-mixing (dry is carried out to above-mentioned active material and hygroscopic matter before above-mentioned steps (1)
Mixing the step of) or mixing (hard mixing) firmly and above-mentioned hygroscopic matter made to be tightly attached to above-mentioned active material surface.
Above-mentioned dry-mixing can not add bonding agent or thickener etc. and mix above-mentioned active material and hygroscopic matter
Realize, it is above-mentioned firmly be blended in there are minute quantity bonding agent or thickener etc. in the case where mix above-mentioned active material at high viscosities
It is realized with hygroscopic matter.
At this point, be located at arranged by above-mentioned active material and the hygroscopic matter in gap that is formed be located at above-mentioned active material
The hygroscopic matter on surface can have the weight ratio of 99.9:0.1 to 80:20, specifically, can have 99.5:0.5 to 90:10's
Weight ratio, more specifically, can have the weight ratio of 99:1 to 95:5.
On the other hand, it is located at above-mentioned hygroscopic matter by between above-mentioned active material arranges and is formed gap and above-mentioned
Method between active material and collector is not particularly limited, for example, can realize by the following method, that is, the above method can
Include: step (1), applies the slurry containing active material on the current collector to form active material layer；And step (2), it will
Dispersion liquid containing hygroscopic matter is permeated in above-mentioned active material layer, and is located at above-mentioned hygroscopic matter by above-mentioned active matter
Matter arranges and between the gap of formation, and before above-mentioned steps (1), additionally including coating on above-mentioned collector makes hygroscopicity
The step of substance and bonding agent are mixed in mixture made of solvent.As needed, the mixture coated on above-mentioned collector can
Additionally comprising conductive agent etc., the amount for being contained in the hygroscopic matter of each position can be by used in each step
The amount of hygroscopic matter be suitably adjusted and adjusted.
Positioned at arranged by above-mentioned active material and above-mentioned hygroscopic matter between the gap that is formed be located at above-mentioned activity
Above-mentioned hygroscopic matter between substance and collector can have the weight ratio of 99.9:0.1 to 80:20, specifically, can have
The weight ratio of 99.5:0.5 to 90:10, more specifically, can have the weight ratio of 99:1 to 95:5.
Make above-mentioned hygroscopic matter be located at by between above-mentioned active material arranges and is formed gap, 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, that is,
The above method includes: step (1), carries out dry-mixing or hard mixing to active material and hygroscopic matter and makes above-mentioned hygroscopicity object
Matter is tightly attached to the surface of above-mentioned active material；And step (2), containing for obtaining from above-mentioned steps (1) are close on surface
There is the slurry coating of the active material of hygroscopic matter in forming active material layer on collector, before above-mentioned steps (2),
Additionally include the step of coating makes hygroscopic matter and bonding agent be mixed in mixture made of solvent on above-mentioned collector.
As needed, the mixture coated on above-mentioned collector can be contained in the hygroscopicity of each position additionally comprising conductive agent etc.
The amount of substance can be adjusted and the amount to the hygroscopic matter used in each step is suitably adjusted.
Positioned at arranged by above-mentioned active material and between the gap that is formed, the surface of above-mentioned active material and above-mentioned active matter
Above-mentioned hygroscopic matter between matter and collector can have the weight ratio of 99.9:0.05:0.05 to 80:10:10, specifically,
There can be the weight ratio of 99.5:0.25:0.25 to 90:5:5, more specifically, there can be 99:0.5:0.5 to 95:2.5:2.5's
Weight ratio.
As described above, the amount of above-mentioned hygroscopic matter is opposite when except above-mentioned hygroscopic matter being also located at above-mentioned gap
There can be the weight ratio of 99.9:0.1 to 80:20 in the hygroscopic matter for being located at above-mentioned gap, be located at except above-mentioned gap
The amount of hygroscopic matter is situations more than 0.1 parts by weight relative to 99.9 parts by weight of the hygroscopic matter for being located at above-mentioned gap
Under, so that a small amount of above-mentioned hygroscopic matter is located at except above-mentioned gap and is increased the effect for absorbing moisture, so that battery can be realized
The raising of performance, the hygroscopic matter being located at except above-mentioned gap amount relative to the hygroscopic matter for being located at above-mentioned gap
80 parts by weight are that can prevent from becoming with the amount for the hygroscopic matter being located at except above-mentioned gap in 20 parts by weight situation below
The problem of increasing the volume of active material layer excessively or thus reducing the energy density of per unit volume.
In the electrode of lithium secondary cell of an example present invention as described above, above-mentioned active material layer may have 3 weights
Amount percentage moisture rate below specifically may have the moisture rate of 0.1 weight percent to 2 weight percent, more specifically
Ground may have the moisture rate of 0.5 weight percent to 1.5 weight percent.
Above-mentioned electrode of lithium secondary cell can be able to be specifically cathode for cathode or anode.
The present invention provides the lithium secondary battery comprising above-mentioned electrode.
Above-mentioned lithium secondary battery may include anode, cathode and the diaphragm between above-mentioned positive electrode and negative electrode.
It, can be according to the above-mentioned hygroscopic matter for being included in the case where including above-mentioned hygroscopic matter in active material layer
Position, above-mentioned anode is manufactured by the manufacturing method of electrode above-mentioned, do not include above-mentioned hygroscopic matter in the case where,
It can be by manufacturing above-mentioned anode in well known usual way in the technical field of the invention, for example, can be in positive-active
Mixed solvent in substance, as needed, mixing bonding agent, conductive agent, dispersing agent are simultaneously stirred and prepare slurry, are inciting somebody to action later
Above-mentioned slurry coating is dried after the collector of metal material and compression and manufactures anode.
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, M1For selected from one of group being made of Al, Ga and In or in which 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 the group of Co, Fe, Cr, V, Cu, Zn and Ti composition, M3For selected from one of group being made of Al, Mg and B with
On, A be selected from one or more of the group being made of P, F, S and N) etc. lamellar compounds or by a kind or a kind or more transition gold
Belong to replaced compound；Li1+hMn2-hO4(in above-mentioned formula, 0≤h≤0.33), LiMnO3、LiMn2O3、LiMnO2Equal lithiums manganese
Oxide；Lithium Cu oxide (Li2CuO2)；LiV3O8、V2O5、Cu2V2O7Equal barium oxides；By chemical formula LiNi1-iM4 iO2(upper
It states in formula, M4=Co, Mn, Al, Cu, Fe, Mg, B or Ga, 0.01≤y≤0.3) indicate Ni mine type lithium nickel oxide；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) indicate 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 however, it is not limited to this.
The collector of the above-mentioned metal material metal high as conductibility, as long as the slurry of above-mentioned positive active material
Material is easy the metal of bonding, the battery will not be made to cause chemical change and the gold with high conductivity in the voltage range of battery
Belong to, be 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
Metal made of being surface-treated with charcoal, nickel, titanium, silver etc..Also, fine bumps can be formed on collector surface to improve
The bonding force of positive active material.Collector can be with a variety of shapes such as film, piece, foil, net, porous plastid, foaming body, non-woven body
State is come using can have 3 μm to 500 μm of thickness.
As the solvent for being used to form above-mentioned anode, there are N-Methyl pyrrolidone (NMP), dimethylformamide (DMF), third
The organic solvents such as ketone, dimethyl acetamide 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 the degree of dispersion.
As above-mentioned bonding agent, Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP) can be used, gather inclined fluorine
Ethylene (polyvinylidenefluoride), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate
(polymethylmethacrylate), polyvinyl alcohol, carboxymethyl cellulose (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 rubbers (SBR), fluorubber, polyacrylic acid (poly acrylic acid) and these
Hydrogen by a variety of bonding agent macromolecules such as Li, Na or Ca etc. substituted macromolecules or a variety of copolymers.
As long as above-mentioned conductive agent will not make the battery cause chemical change and conductive, it is not particularly limited, for example,
The graphite such as natural or artificial graphite can be used；Acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal black etc.
Carbon black；The conducting fibres such as carbon fiber or metallic fiber；The electric conductivity pipe such as carbon nanotube；The gold such as fluorocarbon, aluminium, nickel by powder
Belong to powder；Zinc oxide, the conductive whiskers such as potassium titanate；The conductive metal oxides such as titanium oxide；Hole polyphenylene derivatives etc.
Conductive material etc..
The organic dispersing agents such as water class dispersing agent or N-Methyl pyrrolidone can be used in above-mentioned dispersing agent.
Above-mentioned cathode can be manufactured in the following way, for example, on negative electrode collector by negative electrode active material, conductive agent and
After the mixture of bonding agent mixes with regulation solvent and prepares slurry, by above-mentioned slurry coating on collector, pass through later
It dries and manufactures above-mentioned cathode.
It, can be usually using the carbon that can absorb and discharge lithium ion as the negative electrode active material for being used in above-mentioned cathode
Material, lithium metal, silicon or tin etc..Preferably, can be used carbon material, and as carbon material, can be used low-crystalline carbon and
High crystalline carbon etc..It is representative to have soft carbon (soft carbon) and hard carbon (hard carbon) as low-crystalline carbon, make
It is representative to have natural graphite, kish graphite (kish graphite), pyrolytic carbon for high crystalline carbon
(pyrolyticcarbon), mesophase pitch-based carbon fibers (mesophase pitch based carbon fiber), centre
Phase carbon microspheres (meso-carbon microbeads), mesophase pitch (mesophase pitches) and petroleum and coal class
The high-temperature calcinations 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 be such that the battery draws
Play chemical change and conductive, be just not particularly limited, can be used for example copper, gold, stainless steel, aluminium, nickel, titanium, calcining carbon,
Metal, aluminium-cadmium alloy made of being surface-treated to the surface charcoal, nickel, titanium etc. of copper or stainless steel etc..Also, it can also be with
Form micro concavo-convex on surface to reinforce the engaging force of negative electrode active material, and can with film, piece, foil, net, porous plastid,
The variforms such as foaming body, non-woven body use.
Above-mentioned bonding agent can use to be bonded negative electrode active material particle to maintain formed body, as long as preparing
Used common bonding agent, is just not particularly limited when negative electrode active material slurry, for example, can be used viscous as non-aqueous class
Connect polyvinyl alcohol, carboxymethyl cellulose, hydroxy propylene cellulose, the polyacetylene fibres element, polyvinyl chloride, polyvinylpyrrolidine of agent
Ketone, polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVdF), polyethylene or polypropylene etc., also, can be used selected from by as water
One of group of the acrylonitrile-butadiene rubber of class bonding agent, SBR styrene butadiene rubbers 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, environmentally friendly, and also harmless to the health of staff, and glues
It connects that effect is more excellent than non-aqueous class bonding agent, thus the active material ratio of every same volume can be improved, so that high capacity can be realized
Change, as water class bonding agent, it is preferable that SBR styrene butadiene rubbers can be used.
Above-mentioned bonding agent may include 10 weight percent in the overall weight of negative electrode active material slurry hereinafter, specific
Ground may include 0.1 weight percent to 10 weight percent.If the content of above-mentioned bonding agent is led to less than 0.1 weight percent
Cross using bonding agent and having little effect of generating and not preferably, if the content of above-mentioned bonding agent is more than 10 weight percent,
Because the content of bonding agent increase due to reduces the relative amount of active material, thus there are every volume capacity decline hidden danger and simultaneously
Not preferably.
As long as above-mentioned conductive agent will not make the battery cause chemical change and conductive, it is not particularly limited, for example,
The graphite such as natural or artificial graphite can be used；Acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal black
Equal carbon blacks；The conducting fibres such as carbon fiber or metallic fiber；The metal powders such as fluorocarbons, aluminium, nickel by powder；Zinc oxide, potassium titanate
Etc. conductive whiskers；The conductive metal oxides such as titanium oxide；And conductive materials such as polyphenylene derivatives etc..It is above-mentioned to lead
Electric agent can be used relative to negative electrode active material slurry overall weight be 1 weight percent to 9 weight percent amount.
As the solvent for being used to form above-mentioned cathode, have N-Methyl pyrrolidone (NMP), dimethylformamide (DMF),
The organic solvents such as acetone, dimethyl acetamide 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, prepares yield, as long as can make above-mentioned negative electrode active material, bonding agent, conduction
The degree of agent dissolution and dispersion.
As needed, above-mentioned cathode also may include the thickener for adjusting viscosity.
Above-mentioned thickener can be cellulose compound, for example, can be for selected from by carboxymethyl cellulose (CMC), hydroxyl
The substance of one or more of the group of methylcellulose, hydroxyethyl cellulose and hydroxypropyl cellulose composition, specifically, Ke Yiwei
Above-mentioned negative electrode active material and bonding agent can be dispersed in water to be suitable for by carboxymethyl cellulose (CMC) together with thickener
Cathode.
On the other hand, as diaphragm, the previous common porous polymer membrane for being used as diaphragm can be used, for example, can incite somebody to action
Alathon, Noblen, ethylene-butene copolymer, ethylene-hexene co-polymers and ethylene-methyl acrylate copolymerization
The porous polymer membrane that object etc. is manufactured by polyolefin macromolecular is used alone or they is laminated and uses, or can be used
Common porous nonwoven cloth, for example, can be used by shapes such as dystectic glass fibre, pet fibers
At non-woven fabrics, however, it is not limited to this.
The lithium salts that can include as electrolyte as used in the present invention can be unlimitedly using being typically used in
The substance of secondary lithium batteries electrolyte, for example, the anion as above-mentioned lithium salts, it can be for selected from by F-、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-One of group of composition substance.
As electrolyte of the invention is used in, the organic liquid being able to use when manufacturing lithium secondary battery can be enumerated
Body electrolyte, inorganic liquid electrolyte, solid macromolecule electrolyte, gluey polyelectrolyte, solid inorganic electrolytes and
Fusion inorganic electrolyte etc., however, it is not limited to this.
The shape of lithium secondary battery of the invention is not particularly limited, and can be in use the cylinder-shaped, rectangular of tank, bag
(pouch) shape or coin (coin) shape.
Lithium secondary battery of the invention not only can be used in the secondary battery unit for the power supply for being used as midget plant, Er Qieyou
Selection of land also can be used in the unit cells for the medium-and-large-sized battery model for including multiple secondary battery units.
It is dynamic can to enumerate electric car, mixed power electric car, plug-in mixing for the preference of large-scale plant among the above
Power electric car and accumulating system etc., but be not limited to that this.
Embodiment
Hereinafter, enumerating embodiment and experimental example in order to illustrate the present invention and being illustrated in more detail, but this hair
It is bright to be not limited to these embodiments and experimental example.The embodiment of the present invention can be changed to variform, shall not be construed as this
The range of invention is confined to following embodiments.The embodiment of the present invention is in order to the common skill of the technical field of the invention
Art personnel are more fully explained of the invention and offer.
Embodiment 1: the manufacture of the negative electrode for lithium secondary battery comprising hygroscopic matter
It is the graphite of 25 μm of 86 weight percent to average grain diameter, the second of 1 weight percent as negative electrode active material
The CMC (thickener) of acetylene black (Denka black) (conductive agent), the SBR (bonding agent) of 2 weight percent and 1 weight percent
It is mixed with the NMP as solvent to have prepared negative electrode slurry.By the above-mentioned negative electrode active material slurry prepared with 65 μ
The thickness of m is coated on the one side as copper (Cu) film of 10 μm of negative electrode collectors and forms active material layer, and carries out to it
Drying, later to the average grain diameter (D as hygroscopic matter50) it is 0.5 μm of silica gel to become 1/10 weight of above-mentioned graphite
The mode for measuring the amount of part is mixed with NMP and has prepared mixed liquor, permeates above-mentioned mixed liquor slowly in above-mentioned active matter
Matter layer 30 minutes.If completing the infiltration of mixed liquor, it is dried and is rolled, later with prescribed level is punched out and is made
Cathode is made.
Embodiment 2 is to embodiment 5
Other than the partial size of above-mentioned silica gel is changed to partial size as shown in table 1 below, with identical with above-described embodiment 1
Method has manufactured cathode.
Embodiment 6 is to embodiment 10
In addition to 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 to have manufactured cathode except 0.5 μm of silica gel in method identical with above-described embodiment 1.
Embodiment 11
The average grain diameter of graphite and 1 parts by weight as hygroscopic matter that average grain diameter to 100 parts by weight is 25 μm
(D50) it is the dry-mixing that 0.5 μm of silica gel is carried out 30 minutes with the mixing speed of 25rpm, 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 on surface to 86 weight percent
The CMC (thickener) of the acetylene black (conductive agent) of ratio, the SBR (bonding agent) of 2 weight percent and 1 weight percent with as molten
The NMP of agent is mixed to have prepared negative electrode slurry.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
The one side of copper (Cu) film coated on the negative electrode collector as 10 μm and form active material layer, and it is done
It is dry, later to the average grain diameter (D as hygroscopic matter50) it is 0.5 μm of silica gel to become 9/100 parts by weight of above-mentioned graphite
The mode of amount mixed with NMP to have prepared mixed liquor, permeate above-mentioned mixed liquor slowly in above-mentioned active material layer
30 minutes.If completing the infiltration of mixed liquor, it is dried and is rolled, later with prescribed level is punched out and is manufactured
Cathode.
Embodiment 12
In addition in above-described embodiment 11 use by average grain diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) be
The P of 100nm2O5With the mixture that the weight ratio of 80:20 mixes, to replace the above-mentioned average grain diameter as hygroscopic matter
(D50) it is to have manufactured cathode except 0.5 μm of silica gel in method identical with above-described embodiment 11.
Embodiment 13
To the average grain of the graphite and 3 parts by weight as hygroscopic matter that are 25 μm by the average grain diameter of 100 parts by weight
Diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) be 100nm P2O5With mixture that the weight ratio of 80:20 mixes with
The speed of 25rpm carries out 30 minutes dry-mixings, has thus manufactured and has been glued with above-mentioned silica gel and P on surface2O5Graphite.
As negative electrode active material, above-mentioned silica gel and P are glued with to the surface of 86 weight percent2O5Graphite, 1 weight
The CMC (thickener) and work of the acetylene black (conductive agent) of percentage, the SBR (bonding agent) of 2 weight percent and 1 weight percent
It is mixed for the NMP of solvent and has prepared negative electrode slurry.By the above-mentioned negative electrode active material slurry prepared with 65 μm
Thickness is coated on the one side of copper (Cu) film of the negative electrode collector as 10 μm and forms active material layer, and is done
It is dry, later to by the average grain diameter (D as hygroscopic matter50) it is 2 μm of silica gel and average grain diameter (D50) be 100nm P2O5
It is carried out in a manner of the amount of 7/100 parts by weight of the mixture that the weight ratio of 80:20 mixes to become above-mentioned graphite with NMP
Mixing permeates above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes to have prepared mixed liquor.If completing mixed liquor
Infiltration, then it is dried and is rolled, later with prescribed level is punched out and has manufactured cathode.
Embodiment 14
Silica gel, the acetylene black (conductive agent) of 1 parts by weight and the SBR of 2 parts by weight that partial size to 80 parts by weight is 0.5 μm
(bonding agent) is mixed to have prepared mixture with the NMP as solvent, and said mixture is being applied with 2 μm of thickness
It is dried after the one side of copper (Cu) film as 10 μm of negative electrode collectors.At this point, above-mentioned silica gel use relative to
Above-mentioned graphite as negative electrode active material is the amount of 1/100 parts by weight.
As negative electrode active material, the second of graphite, 1 weight percent that the average grain diameter to 86 weight percent is 25 μm
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 weight percent and 1 weight percent with as solvent
NMP is mixed to have prepared negative electrode slurry.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 coated with said mixture, and it is dried, is used as hygroscopicity object later
Matter, to partial size be 0.5 μm 9/100 parts by weight of the silica gel to become above-mentioned graphite amount in a manner of mixed with NMP and to be made
For mixed liquor has been gone out, permeate above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor,
It is dried and is rolled, later with prescribed level is punched out and has manufactured cathode.
Embodiment 15
In addition in above-described embodiment 14 use by average grain diameter (D50) be 2 μm silica gel and average grain diameter (D50) be
The P of 100nm2O5With the mixture that the weight ratio of 80:20 mixes, to replace the above-mentioned average grain diameter as hygroscopic matter
(D50) it is to have manufactured cathode except 0.5 μm of silica gel in method identical with above-described embodiment 14.
Embodiment 16
To the average grain diameter (D by 80 parts by weight50) be 2 μm silica gel and average grain diameter (D50) be 100nm P2O5With 80:
The acetylene black (conductive agent) of mixture, 1 parts by weight, the SBR (bonding agent) of 2 parts by weight and the conduct that 20 weight ratio mixes
The NMP of solvent is mixed to have prepared mixture, and said mixture is being coated on using 2 μm of thickness as 10 μm of cathode
The one side of copper (Cu) film of collector, later dries it.At this point, said mixture has been used relative to as negative
The above-mentioned graphite of pole active material is the amount of 1/10 parts by weight.
As negative electrode active material, the second of graphite, 1 weight percent that the average grain diameter to 86 weight percent is 25 μm
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 weight percent and 1 weight percent with as solvent
NMP is mixed to have prepared negative electrode slurry.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 coated with said mixture, and it is dried, later to by as moisture absorption
Average grain diameter (the D of property substance50) be 2 μm silica gel and average grain diameter (D50) be 100nm P2O5It is mixed with the weight ratio of 80:20
Made of 9/100 parts by weight of the mixture to become above-mentioned graphite amount in a manner of mixed with NMP to have prepared and mix
Liquid permeates above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor, it is done
It is dry and roll, later with prescribed level is punched out and has manufactured cathode.
Embodiment 17
The silica gel that the partial size of graphite and 0.5 parts by weight that average grain diameter to 100 parts by weight is 25 μm is 0.5 μm is done
Mixing and hard mixing, and manufactured and be glued with the graphite of above-mentioned silica gel on surface.
Silica gel, the acetylene black (conductive agent) of 1 parts by weight and the SBR of 2 parts by weight that partial size to 80 parts by weight is 0.5 μm
(bonding agent) is mixed to have prepared mixture with the NMP as solvent, and said mixture is coated on 2 μm of thickness
It is dried after the one side of Copper thin film as 10 μm of negative electrode collectors.At this point, above-mentioned silica gel used relative to
Above-mentioned graphite as negative electrode active material is the amount of 1/200 parts by weight.
As negative electrode active material, graphite, 1 weight percent of above-mentioned silica gel are glued on surface to 86 weight percent
The CMC (thickener) of the acetylene black (conductive agent) of ratio, the SBR (bonding agent) of 2 weight percent and 1 weight percent with as molten
The NMP of agent is mixed to have prepared negative electrode slurry.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
Active material layer is formed coated on the Copper thin film coated with said mixture, and it is dried, is used as moisture absorption later
Property substance, to partial size be 0.5 μm 9/100 parts by weight of the silica gel to become above-mentioned graphite amount in a manner of mix with NMP
Mixed liquor is prepared, permeates above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes.If completing the infiltration of mixed liquor,
Then it is dried and is rolled, later with prescribed level is punched out and has manufactured cathode.
Embodiment 18
It is different with size as shown in table 1 below and/or type in addition to being used as hygroscopic matter to use in above-described embodiment 17
Hygroscopic matter, be to be prepared except 0.5 μm of silica gel in method identical with above-described embodiment 17 to replace above-mentioned partial size
Cathode.
Embodiment 19
To by the average grain diameter graphite for being 25 μm of 100 parts by weight and the average grain diameter (D of 2 parts by weight50) it is 2 μm of silica gel
With average grain diameter (D50) be 100nm P2O5Dry-mixing and hard has been carried out with the weight ratio of 80:20 come the mixture that mixes
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 parts by weight50) be 2 μm silica gel and average grain diameter (D50) be 100nm P2O5With 80:
The acetylene black (conductive agent) of mixture, 1 parts by weight that 20 weight ratio mixes and the SBR (bonding agent) of 2 parts by weight and work
It is mixed for the NMP of solvent and prepares mixture, said mixture is coated on using 2 μm of thickness as 10 μm of cathode collection
It is dried after the one side of copper (Cu) film of electric body.At this point, above-mentioned silica gel has been used relative to living as cathode
Property substance graphite be 2/100 parts by weight amount.
As negative electrode active material, above-mentioned silica gel and P are glued on surface to 86 weight percent2O5Mixture
Graphite, the acetylene black (conductive agent) of 1 weight percent, the SBR (bonding agent) of 2 weight percent and the CMC of 1 weight percent
(thickener) is mixed to have prepared negative electrode slurry with the NMP as solvent.By the above-mentioned negative electrode active material prepared
Slurry does it so that 65 μm of thickness is coated on the Copper thin film coated with said mixture and forms active material layer
It is dry, it is used as hygroscopic matter later, to by average grain diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) be 100nm P2O5
It is carried out in a manner of the amount of 6/100 parts by weight of the mixture that the weight ratio of 80:20 mixes to become above-mentioned graphite with NMP
Mixing permeates above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes to have prepared mixed liquor.If completing mixed liquor
Infiltration, then it is dried and is rolled, later with prescribed level is punched out and has manufactured cathode.
Embodiment 20
As negative electrode active material, the second of graphite, 1 weight percent that the average grain diameter to 86 weight percent is 25 μm
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 weight percent and 1 weight percent with as solvent
NMP is mixed to prepare negative electrode slurry.The above-mentioned negative electrode active material slurry prepared is coated on 65 μm of thickness
As copper (Cu) film of 10 μm of negative electrode collector one side and form active material layer and it dried, Zhi Houzuo
For hygroscopic matter, to by average grain diameter (D50) it is 2 μm of silica gel and average grain diameter (D50) be 5nm P2O5With the weight of 80:20
It is mixed with NMP in a manner of the amount for measuring 9/100 parts by weight of the mixture than mixing to become above-mentioned graphite to prepare
Mixed liquor out permeates above-mentioned mixed liquor slowly in above-mentioned active material layer 30 minutes.If the infiltration of mixed liquor is completed, to it
It is dried and rolls, later with prescribed level is punched out and has manufactured cathode.
Comparative example 1
The silica gel that the partial size of graphite and 10 parts by weight that average grain diameter to 100 parts by weight is 25 μm is 0.5 μm is done
Mixing and hard mixing, and manufactured and be glued with the graphite of above-mentioned silica gel on surface.
Graphite, 1 weight percent as negative electrode active material, to 86 weight percent for 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 weight percent and 1 weight percent with as molten
The NMP of agent is mixed to have prepared negative electrode slurry.By the above-mentioned negative electrode active material slurry prepared with 65 μm of thickness
One side coated on copper (Cu) film as 10 μm of negative electrode collectors and form active material layer, and it is dried and is pressed
Prolong, later with prescribed level is punched out and has manufactured cathode.
Comparative example 2
Silica gel, the acetylene black (conductive agent) of 1 parts by weight and the SBR of 2 parts by weight that partial size to 80 parts by weight is 0.5 μm
(bonding agent) is mixed to prepare mixture with the NMP as solvent, by said mixture with 2 μm of thickness coated on work
It is dried after one side for copper (Cu) film of 10 μm of negative electrode collectors.
As negative electrode active material, the second of graphite, 1 weight percent that the average grain diameter to 86 weight percent is 25 μm
The CMC (thickener) of acetylene black (conductive agent), the SBR (bonding agent) of 2 weight percent and 1 weight percent with as solvent
NMP is mixed to prepare negative electrode slurry.The above-mentioned negative electrode active material slurry prepared is coated on 65 μm of thickness
Copper thin film coated with said mixture and form active material layer, and it is dried and is rolled, later with prescribed level
It is punched out and has manufactured cathode.
Table 1
Embodiment 1-1 to embodiment 20-1: the manufacture of the lithium secondary battery comprising hygroscopic matter
Make the perforated membrane of the polyethylene agent with a thickness of 17 μm between being manufactured respectively from above-described embodiment 1 into embodiment 20
Cathode and lithium metal between after, mixed by ethylene carbonate (EC) and diethyl carbonate (DEC) with the volume ratio of 30:70
Made of in solution 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
Make the perforated membrane of the polyethylene agent with a thickness of 17 μm between being manufactured respectively from above-mentioned comparative example 1 into comparative example 2
Cathode and lithium metal between after, mixed by ethylene carbonate (EC) and diethyl carbonate (DEC) with the volume ratio of 30:70
Made of in solution 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 obtained from embodiment 1-1 to embodiment 20-1, in comparative example 1-1 and comparative example 2-1 respectively
Half-cell confirms cycle characteristics, implements electrochemical evaluation experiment as follows.
Specifically, to the coin obtained from embodiment 1-1 to embodiment 20-1, in comparative example 1-1 and comparative example 2-1 respectively
Type half-cell is charged at 25 DEG C with the constant current of 0.5C (CC), until its voltage reaches 0.005V, later by perseverance
Constant voltage (CV) carries out 1 charging, until charging current reaches 0.005C (cut-off current: cut-off current).Exist later
It charges after placing 20 minutes by the constant current (CC) of 0.5C, until its voltage reaches 1.5V.By above-mentioned steps with
The mode of circulation implements 1 to 100 time repeatedly.It is shown in FIG. 4 and the capacity of battery is being maintained after 100 circulations
The measurement result that rate is measured.
Referring to Fig. 4, it is known that, process 100 times of the hygroscopic matter big relative to partial size, the small hygroscopic matter of partial size follow
Capacity maintenance rate after ring is more preferable.Specifically, observation embodiment 1-1 to embodiment 4-1's as a result, it is found that if hygroscopicity object
The partial size of matter is small, then improves cycle performance.But it as confirmed from embodiment 5-1, can be confirmed, in moisture absorption
In the case that the partial size of property substance is excessively small, make the consumption of electrolyte big because of the side reaction of the electrolyte in surface, thus
Cycle performance generates bad influence instead.
On the other hand, it can also confirm that, according to the position of hygroscopic matter, the capacity after 100 circulations is tieed up
Holdup changes.Specifically, it if being compared to the result of embodiment 1-1, comparative example 1-1 and 2-1, can be confirmed, i.e.,
Keep the type of hygroscopic matter identical, also according to its position, the capacity maintenance rate after 100 circulations is had differences, especially
Its, in the case where hygroscopic matter is located at gap, relative to hygroscopic matter be located at active material surface or active material with
The case where between collector, capacity maintenance rate is more excellent, and relative to hygroscopic matter between active material and collector
The case where, in the case where being located at active material surface, capacity maintenance rate is relatively excellent.
On the other hand, it is known that, it is mixed by 2 kinds of hygroscopic matters of 2 kinds of hygroscopic matters of different sizes and distinct
In the case where closing use, with the unmixed use the case where compared with, the capacity maintenance rate after 100 circulations is higher.
Claims (17)
- It include active material layer and collector 1. a kind of electrode of lithium secondary cell,The electrode of lithium secondary cell is characterized in that,The active material layer includes active material and hygroscopic matter,The hygroscopic matter be located in the active material layer arranged by the active material and between the gap that is formed,The hygroscopic matter is with 1 μm to 20 μm average grain diameter D50The first hygroscopic matter and have 10nm to 1 μm it is flat Equal partial size D50The second hygroscopic matter mixture,First hygroscopic matter and second hygroscopic matter are mixed with the weight ratio of 60:40 to 99:1.
- 2. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe 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 sieve and 3A molecular sieve, Ba (ClO4)2, crosslinking combine Polyacrylic acid and polyacrylic acid composition one or more of group substance.
- 3. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe average grain diameter D of the active material50It is 0.1 to 30 μm.
- 4. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe size in the gap is 0.01 to 20 μm.
- 5. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe average grain diameter D of the hygroscopic matter50Size be average grain diameter D relative to the active material500.1% to 70%.
- 6. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe hygroscopic matter includes 1 to 20 parts by weight on the basis of the active material of 100 parts by weight.
- 7. electrode of lithium secondary cell according to claim 1, which is characterized in thatFirst hygroscopic matter is selected from the polyacrylic acid combined by silica gel, zeolite, 4A molecular sieve and 3A molecular sieve, crosslinking And the substance of one or more of 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 substance of one or more of the group of composition.
- 8. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe voidage of the active material layer is 10% to 40%.
- 9. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe hygroscopic matter is also additionally located at the surface of the active material other than being located at the gap,It is 99.9 positioned at the hygroscopic matter in the gap and the weight ratio for the hygroscopic matter for being located at the active material surface: 0.1 to 80:20.
- 10. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe hygroscopic matter other than being located at the gap also additionally between the active material layer and collector,Positioned at the hygroscopic matter in the gap and the weight of the hygroscopic matter between the active material layer and collector Amount is than being 99.9:0.1 to 80:20.
- 11. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe hygroscopic matter is other than being located at the gap also additionally positioned at the surface of the active material and the work Between property material layer and collector,Be located at the gap, the active material surface and the active material layer and collector between hygroscopicity object The weight ratio of matter is 99.9:0.05:0.05 to 80:10:10.
- 12. electrode of lithium secondary cell according to claim 1, which is characterized in thatThe moisture rate of the active material layer is 3 weight percent or less.
- 13. a kind of lithium secondary battery includes electrode of lithium secondary cell described in any one of claims 1 to 12.
- 14. a kind of manufacturing method of electrode of lithium secondary cell, comprising:Step (1), applies the slurry containing active material on the current collector and forms active material layer；AndStep (2) permeates the dispersion liquid containing hygroscopic matter in the active material layer, to make the hygroscopic matter Positioned at being arranged between the gap that is formed by the active material, the hygroscopic matter is with 1 μm to 20 μm average grain diameter D50The first hygroscopic matter and have 10nm to 1 μm of average grain diameter D50The second hygroscopic matter mixture, wherein described First hygroscopic matter and second hygroscopic matter are mixed with the weight ratio of 60:40 to 99:1.
- 15. the manufacturing method of electrode of lithium secondary cell according to claim 14, which is characterized in thatIt additionally include that dry-mixing or hard mixing are carried out to the active material and hygroscopic matter before the step (1) And the step of making the hygroscopic matter be tightly attached to the active material surface.
- 16. the manufacturing method of electrode of lithium secondary cell according to claim 14, which is characterized in thatBefore the step (1), additionally including coating on the collector is mixed in hygroscopic matter and bonding agent Made of solvent the step of mixture.
- 17. the manufacturing method of electrode of lithium secondary cell according to claim 16, which is characterized in thatBefore the step (2), additionally including coating on the collector is mixed in hygroscopic matter and bonding agent Made of solvent the step of mixture.
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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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| JP7013876B2 (en) | 2018-01-09 | 2022-02-01 | トヨタ自動車株式会社 | A method for manufacturing a positive electrode plate for a lithium ion secondary battery, a lithium ion secondary battery, and a positive electrode plate for a lithium ion secondary battery. |
| CN109742455B (en) * | 2018-12-24 | 2022-01-18 | 深圳市量能科技有限公司 | Method for manufacturing lithium ion battery |
| KR102333629B1 (en) * | 2019-11-18 | 2021-12-01 | 한국세라믹기술원 | Moisture adsorption filter for gas sensor based on anodic aluminum oxide substrate using ultrasonic spray method and method of manufacturing the same |
| CN112216814B (en) * | 2020-12-09 | 2021-04-27 | 江苏时代新能源科技有限公司 | Electrode plate, secondary battery, preparation method of secondary battery and device containing secondary battery |
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| CN106848379A (en) | 2017-06-13 |
| KR102088858B1 (en) | 2020-03-13 |
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