CN101796671A - Metal oxide-coated positive electrode active material, lithium secondary battery, and manufacture method therefor - Google Patents
Metal oxide-coated positive electrode active material, lithium secondary battery, and manufacture method therefor Download PDFInfo
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- CN101796671A CN101796671A CN200880105510A CN200880105510A CN101796671A CN 101796671 A CN101796671 A CN 101796671A CN 200880105510 A CN200880105510 A CN 200880105510A CN 200880105510 A CN200880105510 A CN 200880105510A CN 101796671 A CN101796671 A CN 101796671A
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- Prior art keywords
- active material
- positive active
- coated
- metal oxide
- coating
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 240
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 192
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title claims description 108
- 229910052744 lithium Inorganic materials 0.000 title claims description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims description 116
- 238000000576 coating method Methods 0.000 claims description 116
- 238000005516 engineering process Methods 0.000 claims description 102
- 239000000463 material Substances 0.000 claims description 98
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- 210000004508 polar body Anatomy 0.000 claims description 35
- 150000004703 alkoxides Chemical class 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 31
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
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- 229910052726 zirconium Inorganic materials 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
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- 101150058243 Lipf gene Proteins 0.000 description 1
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- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
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- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A metal oxide-coated positive electrode active material (1) having a metal oxide coat layer (3) that entirely coats a surface of a positive electrode active material (2) has pores (4) which are connected from the surface of the positive electrode active material (2) to a surface of the metal oxide coat layer (3) and through which lithium ions are allowed to move. The pores are present in the metal oxide coat layer (3) entirely over the surface thereof.
Description
Technical field
The present invention relates to a kind of lithium secondary battery, more specifically, relate to a kind of like this lithium secondary battery, the cycle characteristics of this lithium secondary battery is improved and the reduction of output characteristic is inhibited; The invention still further relates to a kind of positive active material that is coated with metal oxide (material) that is used to form this lithium secondary battery.The invention still further relates to and be used to be coated with the positive active material of metal oxide and the manufacture method and the lithium secondary battery of lithium secondary battery.
Background technology
Follow the miniaturization of PC, video camera, portable phone etc., lithium secondary battery is just being sought as the practicality of these device power supply (DPS)s and application widely, because the energy density height of lithium secondary battery in the equipment relevant with information and the field of communication equipment.In addition, at automotive field, environmental problem and resource problem have quickened the development of electric automobile.Lithium secondary battery also is considered as the power source of electric automobile.
But commercially available in the market lithium secondary battery adopts organic electrolyte solution, and the solvent of this solution (solvent) is an organic solvent.In this lithium secondary battery, positive active material contacts with electrolyte and reacts.Therefore therefore, along with charging cycle and discharge cycles are repeated, positive active material and electrolyte is deterioration gradually, and exists the amount that discharges and recharges to reduce and thereby the possibility that reduces of cycle characteristics.
Therefore, for durability and the cycle characteristics that improves lithium secondary battery, for example, JP-A-2006-156032 discloses a kind of active material, and the surface of this active material is by to jet paraffin oxidation zirconium sol solution such as the powder of cobalt acid lithium and the whole zirconia that is coated with.In this technology, zirconia prevents the active material deterioration, and therefore improves cycle characteristics.Yet, because the whole coating active material of zirconia surface, therefore there are the situations such as diffusion velocity reduction of lithium ion, and the insertion of lithium ion and the disengaging mobile difficulty that becomes of difficulty or lithium ion that becomes, make the output characteristic of lithium secondary battery reduce.
On the other hand, JP-A-2005-78800 discloses a kind of active material, and the surface of this active material is by being that active material is mixed into metal alkoxide solution and sintered mixture and topical application has metal afterwards with LiMnO.In this technology, the local metal coating that covers the active material surface has suppressed the reactivity between active material and the electrolyte solution, and therefore improves cycle characteristics.But because metal coating is positioned on the part on active material surface, therefore existence can not fully suppress the deterioration of active material and electrolyte solution and can not obtain enough cycle characteristicss owing to the reaction between active material and the electrolyte solution.
Summary of the invention
The invention provides the lithium secondary battery that a kind of cycle characteristics is improved and the reduction of output characteristic is inhibited, a kind of positive active material that is coated with metal oxide that is used to form this lithium secondary battery, and be used for lithium secondary battery and the manufacture method that is coated with the positive active material of metal oxide.
The positive active material that is coated with metal oxide according to first aspect present invention is a kind of like this positive active material of metal oxide, it has the coating of metal oxides with the surperficial whole coating of positive active material, be provided with the hole that is communicated to the surface of described coating of metal oxides from the described surface of described positive active material with whole surface in the described coating of metal oxides, allow lithium ion to move by described hole.
According to the above-mentioned positive active material that is coated with metal oxide of first aspect, described hole is arranged in the described coating of metal oxides equably.
According to first aspect, because the whole metal oxide that is coated with in positive active material surface, thus can suppress positive active material effectively because the deterioration that causes with reaction such as electrolyte solution, and so improve cycle characteristics.In addition, in coating of metal oxides, the hole (hereinafter being sometimes referred to as " intercommunicating pore ") that is communicated to the coating of metal oxides surface from the positive active material surface is provided with equably, wherein allows lithium ion to move by described hole.Therefore therefore, lithium ion can move in intercommunicating pore, and can suppress owing to the reduction that is coated with the output characteristic that metal oxide causes.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the density that is formed on the described hole in the described coating of metal oxides can be at 10 to 1000000/μ m
2Scope in.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the density that is formed on the described hole in the described coating of metal oxides is at 1000 to 10000/μ m
2Scope in.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the size in described hole is in the scope of 0.1nm to 100nm.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the size in described hole is in the scope of 1nm to 10nm.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the film thickness of described coating of metal oxides is in the scope of 1nm to 1000nm.
In addition, in the positive active material that is coated with metal oxide according to first aspect, the film thickness of described coating of metal oxides is in the scope of 10nm to 100nm.
Lithium secondary battery according to second aspect present invention is equipped with the above-mentioned positive active material that is coated with metal oxide.
According to second aspect, can improve cycle characteristics and suppress the positive active material that is coated with metal oxide that output characteristic reduces because used, therefore can provide a kind of and improve cycle characteristics and suppress the lithium secondary battery that output characteristic reduces.
The manufacture method of positive active material that is used to be coated with metal oxide according to third aspect present invention comprises: carry out sol-gel technology, described sol-gel technology forms the gel coating film on the surface of positive active material, in described gel coating film, disperse and be attached with metallo-organic compound and form material with the hole of described metallo-organic compound phase-splitting, and
Carry out sintering process, the described gel coating film that obtains in described sol-gel technology by sintering decomposes and removes described hole and forms material, with on the described surface of described positive active material, form coating of metal oxides, in described coating of metal oxides, on the whole described surface of described positive active material, form the hole, allow lithium ion to move by described hole.
In addition, in manufacture method according to the third aspect, form in described sol-gel technology that wherein said metallo-organic compound and described hole form that material is evenly dispersed and the described gel coat film that adheres to and be formed uniformly described hole in the described coating of metal oxides in described sol-gel technology by the described gel coat film that sintering obtains.
According to the third aspect, can obtain the positive active material that is coated with metal oxide as described below.In other words, because the whole metal oxide that is coated with in positive active material surface, so positive active material is because the deterioration that causes with reaction such as electrolyte solution is suppressed and cycle characteristics is improved.In addition, because the intercommunicating pore from the positive active material surface to the coating of metal oxides surface exists the coating of metal oxides equably, therefore, lithium ion can move in intercommunicating pore, and owing to is coated with the reduction of the output characteristic that metal oxide causes and is inhibited.
In addition, in the manufacture method of positive active material that is used for being coated with metal oxide according to the third aspect, described metallo-organic compound is a metal alkoxide.
In addition, in the manufacture method of positive active material that is used for being coated with metal oxide according to the third aspect, it is polyvinyl alcohol that described hole forms material.
In addition, in the manufacture method of positive active material that is used for being coated with metal oxide according to the third aspect, the number-average molecular weight of described polyvinyl alcohol is in 100 to 10000 scope.
In addition, in the manufacture method of positive active material that is used for being coated with metal oxide according to the third aspect, the number-average molecular weight of described polyvinyl alcohol is in 500 to 2000 scope.
Comprise that according to the manufacture method that is used for lithium secondary battery of fourth aspect present invention use makes the positive electrical polar body by the positive active material that is coated with metal oxide that the above-mentioned manufacture method that is used to be coated with the positive active material of metal oxide obtains.
According to fourth aspect, use obtains by above-mentioned manufacture method can providing a kind of lithium secondary battery that can improve cycle characteristics and suppress the reduction of output characteristic so that can improve cycle characteristics and suppress the positive active material that is coated with metal oxide that output characteristic reduces.
In the present invention, a kind of positive active material that is coated with metal oxide can be provided, the deterioration that it causes by effective inhibition positive active material because with reaction such as electrolyte solution has been improved cycle characteristics and by allowing lithium ion mobile reduction that has suppressed output characteristic in coating of metal oxides.
Description of drawings
From can more understand above-mentioned and/or other purpose of the present invention, feature and advantage below in conjunction with the accompanying drawing description of a preferred embodiment, identical Reference numeral is used to represent components identical in the accompanying drawing, wherein:
Fig. 1 schematically shows the general section view of example of metal oxide-coated state that the present invention is coated with the positive active material of metal oxide;
Fig. 2 illustrates the key diagram of surface state that the present invention is coated with the positive active material of metal oxide;
Fig. 3 is the general section view that schematically shows the example of lithium secondary battery of the present invention;
Fig. 4 illustrates to be used for the making flow chart of example of manufacture method that the present invention is coated with the positive active material of metal oxide;
Fig. 5 is the process chart that the example of sol-gel technology of the present invention is shown; And
Fig. 6 is the making flow chart that the example of the manufacture method that is used for lithium secondary battery of the present invention is shown.
Embodiment
Describe the embodiment that is coated with positive active material, lithium secondary battery and their manufacture method of metal oxide of the present invention below in detail.
Describe the embodiment that is coated with the positive active material of metal oxide of the present invention below in detail.The positive active material that is coated with metal oxide of the present invention is a kind of like this positive active material that is coated with metal oxide, it has positive active material, and coating of metal oxides, this coating of metal oxides is with the whole surface-coated of positive active material, and has a hole that the surface with the surface of positive active material and coating of metal oxides is communicated with, lithium ion can move by described hole, and described hole is arranged in the coating of metal oxides equably.
According to the present invention, because the whole surface-coated of positive active material has metal oxide, therefore can suppress effectively because the deterioration of the positive active material that the reaction between positive active material and the electrolyte solution etc. causes, and can suppress the deterioration of electrolyte solution, to improve cycle characteristics.In addition, in coating of metal oxides, be provided with the hole that is communicated to the surface of coating of metal oxides from the surface of positive active material equably, lithium ion can move in described hole.Therefore, because lithium ion can move and take place equably moving of lithium ion on the positive active material surface in intercommunicating pore, so can suppress owing to the reduction that is coated with the output characteristic that metal oxide causes.
Fig. 1 schematically shows the general section view of example of metal oxide-coated state that the present invention is coated with the positive active material of metal oxide.As shown in Figure 1, the positive active material 1 that is coated with metal oxide of the present invention has positive active material 2, with coating of metal oxides 3, the surface of coating of metal oxides 3 whole coating positive active materials 2, the hole 4 that is communicated to the surface of coating of metal oxides from the surface of positive active material 2 exists the coating of metal oxides 3 equably, and lithium ion can move by hole 4.In addition, shown in the specification of surface state of positive active material that illustrating of Fig. 2 is coated with metal oxide, the surperficial whole coating of metal oxides 3 that is coated with of positive active material 2, the hole 4 that is communicated to the surface of coating of metal oxides 3 from the surface of positive active material 2 is present in the coating of metal oxides 3 equably, and lithium ion can move by hole 4.Hereinafter, each formation that is coated with the positive active material of metal oxide of the present invention separately is described.
At first, the coating of metal oxides that uses among the present invention is described.The coating of metal oxides that uses among the present invention is arranged on the whole surface of positive active material, and have the hole that the surface from positive active material that exists in even mode is communicated to the surface of coating of metal oxides, lithium ion can move in described hole.The coating of metal oxides of She Zhiing can effectively suppress because the deterioration of the positive active material that the reaction of positive active material and electrolyte solution etc. causes by this way, and can suppress the deterioration of electrolyte solution, improves cycle characteristics thus.In addition, in coating of metal oxides, have the hole that is communicated to the surface of coating of metal oxides from the surface of positive active material equably, lithium ion can move in described hole.Therefore, owing in the surface of positive active material, guaranteed the lithium ion conduction path equably, so can suppress owing to be coated with the reduction of the output characteristic that metal oxide causes.
The metal oxide that uses in the coating of metal oxides is not particularly limited, the deterioration that causes with reaction such as electrolyte solution as long as this metal oxide can effectively suppress positive active material and so can improve cycle characteristics.The example of metal oxide comprises by M
1O
xThe metal oxide of expression.Particularly, metal oxide is meant such metal oxide, wherein metal M
1Be zirconium, tungsten, titanium, boron, aluminium, gallium etc.More specifically, the example of metal oxide comprises zirconia (ZrO
2), tungsten oxide (WO
3), titanium oxide (TiO
2), boron oxide (B
2O
3), aluminium oxide (Al
2O
3) or gallium oxide (Ga
2O
3).Especially, the oxide M of being quoted
1O
xComprise zirconia (ZrO
2), tungsten oxide (WO
3), titanium oxide (TiO
2).These oxides are height aspect surface acidity, and good aspect lithium ion conduction.
The film thickness of coating of metal oxides is not particularly limited, as long as film thickness is approximately such film thickness, when having this film thickness, can effectively suppress positive active material because the deterioration that causes with reaction such as electrolyte solution, and in addition, in coating of metal oxides, there is the hole that is communicated to the surface of coating of metal oxides from the surface of positive active material equably, makes lithium ion can move through described hole.Particularly, preferably, film thickness is in the scope of 1nm to 1000nm, particularly in the scope of 10nm to 100nm.If less than above-mentioned scope, there is the possibility that is difficult to whole coated metal oxide coating on the positive active material surface in film thickness.On the other hand, if greater than above-mentioned scope, there is the possibility that is difficult to be formed uniformly intercommunicating pore in coating of metal oxides in film thickness.
In the present invention, the film thickness of coating of metal oxides can be a value of utilizing electron microscope to measure based on graphical analysis.
In addition, coating of metal oxides has the hole that the surface from positive active material that exists in uniform mode is communicated to the surface of coating of metal oxides, and lithium ion can move in described hole.Described hole is not particularly limited, as long as these holes are present in the coating of metal oxides equably and be communicated to the coating of metal oxides surface from the surface of positive active material, and has the size that allows lithium ion to move through.In the present invention, the meaning of statement " these holes are present in the coating of metal oxides equably " or similar statement for example is that the quantity of per unit area mesopore in the arbitrary portion of coating of metal oxides is always at 10 to 1000000/μ m
2Scope in.Particularly, the meaning of this statement is that the quantity of per unit area mesopore in the arbitrary portion of coating of metal oxides is always at 100 to 10000/μ m
2Scope in, especially at 1000 to 10000/μ m
2Scope in.
By the way, in the present invention, the quantity in hole can be the value of utilizing electron microscope to measure based on graphical analysis.
In addition, the size in hole is not particularly limited, and can move through described hole as long as the size in hole satisfies lithium ion.For example, preferably, the size in hole is in the scope of 0.1nm to 100nm, and especially, the size in hole is in the scope of 1nm to 10nm.If the size in hole is less than above-mentioned scope, the possibility that exists lithium ion to be difficult to move.On the other hand, if the possibility that the ratio that the size in hole greater than above-mentioned scope, exists electrolyte solution etc. contact with the positive active material surface increases, and therefore existence is difficult to suppress the possibility of the deterioration of positive active material.
By the way, in the present invention, the size in hole can be a value of utilizing electron microscope to measure based on graphical analysis.
In addition, the aforementioned apertures among the present invention is present in the coating of metal oxides equably, and is communicated to the coating of metal oxides surface from positive active material.Can check the existence of intercommunicating pore/do not exist by utilizing observations such as electron microscope.
Next the positive active material that uses among the present invention is described.As shown in Figure 1, the positive active material 2 that uses among the present invention is coated with coating of metal oxides 3 on its whole surface.
Positive active material is not particularly limited, as long as described material allows coating of metal oxides attached thereto, and can carefully hide and emit lithium ion.Example at this positive active material of quoting comprises by general formula Li
xM
2O
y, general formula Li
xM
yPO
4, general formula Li
xM
ySiO
4Material Deng expression.Especially can use by general formula Li
xM
2O
yThe material of expression.At general formula Li
xM
2O
yIn, M
2Mainly form, and comprise at least a among Co, Mn, Ni, V and the Fe by transition metal.In addition, at general formula Li
xM
2O
yIn, the value of x and y is at x=0.02 to 2.2, in the scope of y=1.4 to 3.Particularly, it is preferred comprising positive active material at least a among Co, Ni and the Mn.
The shape of positive active material is not particularly limited, as long as its shape allows coating of metal oxides to be attached on the positive active material and allows occlusion and emit lithium ion.For example, the shape of positive active material can be spherical, oval-shaped, or the like.In addition, what can envision is that the mean particle diameter of positive active material is for example in the scope of 0.01 μ m to 10 μ m, especially in the scope of 0.01 μ m to 0.1 μ m.If less than above-mentioned scope, there is the possibility that is difficult to be formed uniformly intercommunicating pore in coating of metal oxides in above-mentioned mean particle diameter.On the other hand, if greater than above-mentioned scope, there is the possibility that is difficult to be provided with coating of metal oxides on the whole surface of positive active material in mean particle diameter.
In the present invention, the mean particle diameter of positive active material can be to utilize for example value measured based on graphical analysis such as SEM of electron microscope.
This method is used for the manufacture method that the present invention is coated with the positive active material of metal oxide and is not particularly limited, as long as can provide a kind of positive active material that is coated with metal oxide that improves cycle characteristics and suppress the requirement that output characteristic reduces.The example of described method comprises that being used to of the following describes is coated with the manufacture method etc. of the positive active material of metal oxide.
The application that is coated with the positive active material of metal oxide of the present invention is not particularly limited.For example, be coated with the positive active material of metal oxide can be as automobile with the positive active material that uses in the lithium secondary battery etc.
Next the embodiment of lithium secondary battery of the present invention is described.Lithium secondary battery of the present invention is characterised in that to have above-mentioned positive active material.
According to the present invention, can improve above-mentioned cycle characteristics and suppress the positive active material that is coated with metal oxide that output characteristic reduces by using, can obtain to improve cycle characteristics and suppress the lithium secondary battery that output characteristic reduces.
Next, accompanying drawings lithium secondary battery of the present invention.Fig. 3 is the general section view that schematically shows the example of lithium secondary battery of the present invention.Lithium secondary battery among Fig. 3 comprises: positive electrical polar body 7, this positive electrical polar body 7 have positive electrode collector 5 and comprise the anodal layer 6 of the positive active material (not shown) that is coated with metal oxide; Negative electricity polar body 10, this negative electricity polar body 10 have negative electrode collector 8 and comprise the negative electrode layer 9 of negative electrode active material (not shown); Be arranged on the dividing plate 11 between positive electrical polar body 7 and the negative electricity polar body 10; The electrolyte (not shown) that comprises lithium salts with filling in anodal layer 6, negative electrode layer 9 and dividing plate 11.The formation according to lithium secondary battery of the present invention of structure by this way hereinafter separately is described.
The following describes the positive electrical polar body that uses among the present invention.The positive electrical polar body that uses among the present invention comprises positive electrode collector at least, comprises the anodal layer and the electrolyte of the positive active material that is coated with metal oxide.
The positive active material that is coated with metal oxide herein is identical with above-mentioned explanation, therefore omits its explanation.
Anodal layer comprises electric conducting material and attachment material usually.The example of electric conducting material comprises carbon black, acetylene black etc.Attachment material is not particularly limited, as long as it is a normally used attachment material in the lithium secondary battery.The concrete example of attachment material comprises Kynoar (PVDF), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), fluorine resin etc.
Positive electrode collector is carried out the current collection of anodal layer.The material of positive electrode collector is not particularly limited, as long as it has conductivity.The example of these materials comprises aluminium, SUS, nickel, iron, titanium etc.Particularly, aluminium and SUS are preferred.Positive electrode collector can be the compact metal collector body, perhaps also can be porous matter metal current collector.
Next the negative electricity polar body that uses among the present invention is described.The negative electricity polar body that uses among the present invention comprises negative electrode collector at least, comprises the negative electrode layer and the electrolyte of negative electrode active material.
Negative electrode active material is not particularly limited, as long as this material can occlusion and emitted lithium ion.The example of negative electrode active material comprises for example graphite etc. of lithium metal, lithium alloy, metal oxide, metal sulfide, metal nitride and carbon-based material.Especially, quote the example of graphite as negative electrode active material.
As required, negative electrode layer can comprise electric conducting material and attachment material.That uses in electric conducting material and attachment material and the anodal layer as used herein is identical.
In addition, negative electrode collector is carried out the current collection of negative electrode layer.The material of negative electrode collector is not particularly limited, as long as this material has conductivity.The example of this material comprises copper, stainless steel, nickel etc.Especially, quote copper as an example.Above-mentioned negative electrode collector can be the compact metal collector body, perhaps also can be porous matter metal current collector.
Next the dividing plate that uses among the present invention is described.The dividing plate that uses among the present invention is arranged between anodal layer and the negative electrode layer, and has the electrolytical function of aforesaid maintenance.The material of dividing plate is not particularly limited.The example of this material comprises resin, for example polyethylene (PE), polypropylene (PP), polyester, cellulose, polyamide etc.Especially, quote polyethylene as an example.In addition, dividing plate can have single layer structure, perhaps can also have sandwich construction.The example of sandwich construction dividing plate comprises the dividing plate etc. of three-decker of dividing plate, the PP/PE/PP of the double-layer structure of PE/PP.And in the present invention, dividing plate can be by perforated membrane, or nonwoven fabrics (for example resin nonwoven fabrics or glass fibre non-woven) etc. is made.
In the present invention, anodal layer described above, negative electrode layer and dividing plate all have the electrolyte that comprises lithium salts.Particularly, described electrolyte can be liquid, perhaps also can be gel state, and can suitably select according to the kind of expectation battery.Especially, Ye Tai electrolyte is preferred.Liquid electrolyte provides good lithium-ion-conducting.Under the situation that electrolyte is in a liquid state, non-aqueous electrolytic solution is preferred.Non-aqueous electrolytic solution provides good lithium-ion-conducting.Non-aqueous electrolytic solution has lithium salts and nonaqueous solvents usually.Lithium salts is not limited especially, so long as lithium salts commonly used gets final product in the lithium secondary battery.The example of lithium salts comprises LiPF
6, LiBF
4, LiN (CF
3SO
2)
2, LiCF
3SO
3, LiC
4F
9SO
3, LiC (CF
3SO
2)
3, LiCIO
4Deng.On the other hand, nonaqueous solvents is not particularly limited, as long as it can dissolve lithium salts.The example of nonaqueous solvents comprises propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, acetonitrile, propionitrile, oxolane, 2-methyltetrahydrofuran, dioxane, 1,3-diox, nitric acid methane, N, dinethylformamide, methyl-sulfoxide, sulfolane, gamma-butyrolacton etc.In the present invention, can use only a kind of in these nonaqueous solventss, perhaps can also use two or more the mixture in these nonaqueous solventss.In addition, non-aqueous electrolytic solution can be the normal temperature fuse salt as used herein.
In lithium secondary battery of the present invention, lithium secondary battery shown in Figure 3 is inserted in the battery container, and processes an opening rim with the sealing opening.Thereby, make lithium secondary battery.The normally metal housing of battery container as used herein, its example comprises the housing that stainless steel is made etc.In addition, the shape of the battery container that uses among the present invention is not particularly limited, as long as battery container can hold aforementioned barriers, above-mentioned anodal layer, above-mentioned negative electrode layer etc.Particularly, the example of the shape of battery container comprises tubular, square, coin shape, sheet etc.
The manufacture method that is used for lithium secondary battery of the present invention is not particularly limited, as long as this method can provide a kind of lithium secondary battery that improves cycle characteristics and suppress the expectation of output characteristic reduction.The example of this manufacture method comprises the manufacture method that is used for lithium secondary battery as described below etc.
The application of lithium secondary battery of the present invention is not particularly limited.For example, lithium secondary battery of the present invention can be as automobile with lithium secondary battery etc.
Describe in detail below and be used for the embodiment of manufacture method that the present invention is coated with the positive active material of metal oxide.Fig. 4 illustrates the example (being coated with the making flow process of the positive active material of metal oxide) of the flow chart of the manufacture method that is used for the positive active material that is coated with metal oxide of the present invention.As shown in Figure 4, be used for the manufacture method that the present invention is coated with the positive active material of metal oxide, carry out sol-gel technology, described sol-gel technology forms the gel coating film on the positive active material surface, evenly disperse in described gel coating film and be attached with metallo-organic compound and form material (hereinafter abbreviate the hole sometimes as and form material) with the hole of described metallo-organic compound phase-splitting.Afterwards, carry out sintering process, the described gel coating film that obtains in described sol-gel technology by sintering decomposes and removes described hole and forms material, and therefore on the positive active material surface, form coating of metal oxides, in described coating of metal oxides, be formed uniformly porosely, allow lithium ion to move by described hole.Like this, can obtain the positive active material that is coated with metal oxide of aforesaid expectation.
According to the present invention, by above-mentioned technology, the positive active material surface can wholely be coated with metal oxide, so as positive active material because the deteriorations that cause with reaction such as electrolyte solution etc. are effectively suppressed and so cycle characteristics be improved.And, owing to the intercommunicating pore from the positive active material surface to the coating of metal oxides surface can be configured to be presented on the coating of metal oxides equably, so lithium ion can move in above-mentioned intercommunicating pore.Thereby, can obtain wherein (metal oxide causes owing to being coated with) output characteristic and reduce the positive active material that is coated with metal oxide that is inhibited.In addition,, can synthesize the positive active material that is coated with metal oxide of expectation at low temperatures, thereby realize to reduce the advantage of making institute's energy requirement by using sol-gel process.
The manufacture method that the aforesaid the present invention of being used for is coated with the positive active material of metal oxide is not particularly limited, as long as this method comprises above-mentioned sol-gel technology and above-mentioned sintering process at least.Manufacture method of the present invention can also comprise other technology.Describe in detail below and be used for each technology of manufacture method that the present invention is coated with the positive active material of metal oxide.
Sol-gel technology among the present invention is described.Sol-gel technology among the present invention is meant the technology shown in the making flow process of the positive active material that is coated with metal oxide of Fig. 4, also be, be coated with the technology of the positive active material of gel by the sol-gel technology preparation, wherein, on the positive active material surface, be formed with the gel coating film, in described gel coating film, disperse equably and be attached with metallo-organic compound and form material with the hole of described metallo-organic compound phase-splitting.Be coated with in the sintering process that the positive active material of gel illustrated hereinafter and use.In sol-gel technology, disperse equably and adhere to the state that is meant with such and adhere to, make the positive active material that is coated with metal oxide that can obtain to have the hole of expectation by the sintering in the sintering process of hereinafter explanation.Sol-gel technology is not particularly limited, as long as it is that a kind of sol-gel process that is coated with the positive active material of gel can be provided, be coated with in the positive active material of gel at this, on the surface of positive active material, form the gel coating film, in described gel coating film, disperse at least equably and be attached with metallo-organic compound and form material with the hole of described metallo-organic compound phase-splitting.For example, can use sol-gel process commonly used.More specifically, the example of sol-gel technology comprises the method shown in the sol-gel technology flow process of Fig. 5, this method comprises: colloidal sol preparation technology, and this colloidal sol preparation technology reaches the scheduled time colloidal sol is provided by for example above-mentioned metallo-organic compound, above-mentioned hole being formed material and above-mentioned positive active material and add predetermined solvent and stirring the mixture under predetermined temperature; After colloidal sol preparation technology, carry out the filtering technique that filters; Gelation technology, this gelation technology by after filtering technique under predetermined temperature the dry mixture that is filtered reach the scheduled time positive active material that is coated with gel be provided.The example of sol-gel technology also comprises other method.
Above-mentioned sol-gel technology is not particularly limited, as long as this technology comprises above-mentioned colloidal sol preparation technology, above-mentioned filtering technique and above-mentioned gelation technology at least.Sol-gel technology can also comprise one or more other technologies.Technology in the sol-gel technology of the present invention hereinafter is described.
Colloidal sol preparation technology in the sol-gel technology shown in Figure 5 is a kind of like this technology, and this colloidal sol preparation technology reaches the scheduled time colloidal sol is provided by for example metallo-organic compound, hole being formed material and positive active material and add predetermined solvent and stirring the mixture under predetermined temperature.Colloidal sol is preparation technology be not particularly limited, as long as this technology can access the colloidal sol that the positive active material that is coated with gel of above-mentioned expectation is provided after filtering technique and gelation technology.For example, can use colloidal sol preparation technology commonly used.More specifically, for example,, and carry out and stir the metallo-organic compound adding predetermined solvent of scheduled volume.Afterwards, the hole of dissolving scheduled volume forms material, and carries out and stir.Afterwards, add the positive active material of scheduled volume, and carry out and stir.A kind of like this method that is used to provide colloidal sol can be used as colloidal sol preparation technology's example.
The metallo-organic compound that uses among the colloidal sol preparation technology is not particularly limited, as long as this compound can obtain the positive active material that is coated with gel of expectation by sol-gel process, wherein, on the positive active material surface, form the gel coating film, the hole formation material that in described gel coating film, disperses equably and be attached with metallo-organic compound and the following describes.Particularly, metal-organic example comprises metal alkoxide, metal oxygen-containing nitrate, nitrate, acetate, sulfate, carbonate, hydroxide, acid etc.Especially, quote metal alkoxide as example.This is because metal alkoxide is commonly used and versatility is high.The M that mentions when above-mentioned metal and explanation are coated with the coating of metal oxides of positive active material of metal oxide
1O
xIn metal M
1Identical, omit its explanation at this.
In colloidal sol preparation technology, metal-organic content forms the variations such as kind, solvent types of the kind of material, metal-organic kind, positive active material in the predetermined solvent based on the hole, and be not particularly limited, as long as its content allows to obtain by sol-gel technology the positive active material that is coated with gel of above-mentioned expectation, and obtain the positive active material that is coated with metal oxide of expectation after the sintering process of explanation below.For example, forming material in the hole is that polyvinyl alcohol (PVA), metallo-organic compound are that metal alkoxide and solvent are under the situation of ethanol series solvent, preferably, metal-organic content is set at percentage by weight in 1 to 50% scope in the predetermined solvent, and especially percentage by weight is in 5 to 30% scope.If less than above-mentioned scope, there is the possibility that is difficult at the positive active material whole metallizing organic compound in surface (metal alkoxide) in the content of metallo-organic compound (metal alkoxide).On the other hand, if content greater than above-mentioned scope, exists the hole that is difficult to disperse equably to become with the metallo-organic compound phase-splitting in metallo-organic compound (metal alkoxide) to form material and the hole is formed the possibility that material is attached to the positive active material surface.
The hole of using among the colloidal sol preparation technology forms material and is not particularly limited, as long as this material can become and the metallo-organic compound phase-splitting, and can be disperseed and be attached to the positive active material surface equably.In addition, the hole forms that material can change based on the kind of metallo-organic compound, positive active material, solvent etc. and can determine by preliminary experiment etc.This preliminary experiments etc. can use a kind of like this material to form material as the hole, and described a kind of material can be by carrying out the positive active material that is coated with metal oxide that formation such as sintering have the hole of expectation.For example, be used as under metallo-organic compound and the situation of ethanol series solvent as above-mentioned solvent at metal alkoxide, polyvinyl alcohol quotabilities such as (PVA) forms the example of material as hole to be used.
The molecular weight of polyvinyl alcohol is based on the weight change of solvent etc., and preferably, the number-average molecular weight of polyvinyl alcohol is in 100 to 10000 scope, especially in 500 to 2000 scope.If number-average molecular weight is too small, there is the possibility that bore dia becomes too small and lithium ion is difficult to move.On the other hand, if number-average molecular weight is excessive, exist bore dia to become possibility that ratio excessive and therefore contact positive active material surface such as electrolyte solution increases, and therefore have the possibility of the deterioration that is difficult to suppress positive active material.
In colloidal sol preparation technology, the hole that adds above-mentioned solvent forms the amount of material based on variations such as the kind of hole formation material, metal-organic kind, the kind of positive active material, above-mentioned solvent types.The amount that added hole forms material is not particularly limited, and becomes and the metallo-organic compound phase-splitting as long as described amount allows the hole to form material, and becomes and disperse equably and be attached to the positive active material surface.For example, forming material in the hole is that polyvinyl alcohol (PVA), metallo-organic compound are that metal alkoxide and above-mentioned solvent are under the situation of ethanol series solvent, preferably, the content that the predetermined solvent mesopore forms material (PVA) is set at percentage by weight in 5 to 50% scope, and especially percentage by weight is in 5 to 30% scope.If the hole forms the content of material (PVA) less than above-mentioned scope, exist to be difficult in metallo-organic compound (metal alkoxide), disperse equably hole to form material and the hole is formed the possibility that material is attached to the positive active material surface with the metallo-organic compound phase-splitting.On the other hand, if the hole forms the content of material (PVA) greater than above-mentioned scope, there is the possibility that is difficult at the positive active material whole metallizing organic compound in surface (metal alkoxide).For example, preferably, the mass ratio (that is, the hole forms material (PVA)/metallo-organic compound (metal alkoxide)) that the hole forms material (PVA) and metallo-organic compound (metal alkoxide) specifically is set in the scope of 1/10 to 3/1 (w/w), especially in the scope of 1/3 to 1/1 (w/w).If this mass ratio (hole forms material (PVA)/metallo-organic compound (metal alkoxide)) is less than above-mentioned scope, the possibility that has adequate relief pore-forming (by described hole, lithium ion can move) in the sintering process that is difficult to illustrate below in the positive active material surface.On the other hand, if greater than above-mentioned scope, there is the possibility that is difficult at the positive active material whole metallizing organic compound in surface (metal alkoxide) in mass ratio.
Positive active material among the colloidal sol preparation technology is not particularly limited, as long as this material can obtain to be coated with the positive active material of gel by sol-gel process, be coated with in the positive active material of gel at this, on the surface of positive active material, form the gel coating film, in described gel coating film, disperse equably and be attached with metallo-organic compound and form material with the hole of described metallo-organic compound phase-splitting.That mentions when the concrete example of positive active material and explanation are coated with the positive active material of positive active material of metal oxide is identical, omits its explanation at this.
In addition, in colloidal sol preparation technology, the amount that adds the positive active material of above-mentioned solvent forms variations such as the kind of material, metal-organic kind, above-mentioned solvent types based on the kind of positive active material, hole.The amount that adds the positive active material of above-mentioned solvent is not particularly limited, as long as metallo-organic compound and form material with the hole of metallo-organic compound phase-splitting and can disperse and be attached to the positive active material surface equably.For example, forming material in the hole is that polyvinyl alcohol (PVA), metallo-organic compound are that metal alkoxide and above-mentioned solvent are under the situation of ethanol series solvent, preferably, the content of positive active material is set at percentage by weight in 10 to 95% scope in the predetermined solvent, and especially percentage by weight is in 40 to 80% scope.If the content of positive active material less than above-mentioned scope, exists the metallo-organic compound (metal alkoxide) of surplus and hole to form the possibility that material (PVA) can form impurity.On the other hand, if greater than above-mentioned scope, existing, the content of positive active material is difficult at positive active material surface whole metallizing organic compound (metal alkoxide) and is difficult in metallo-organic compound (metal alkoxide), disperse equably form the possibility that material is attached to the positive active material surface with the hole formation material of metallo-organic compound phase-splitting with the hole.In addition, preferably, the mass ratio of the gross mass of positive active material and metallo-organic compound (metal alkoxide) and hole formation material (PVA) (promptly, positive active material/(metallo-organic compound (metal alkoxide)+hole forms material (PVA))) specifically be set in the scope of 1/1 to 1000000/1 (w/w), especially in the scope of 3/1 to 100/1 (w/w).If this mass ratio (positive active material/(metallo-organic compound (metal alkoxide)+hole forms material (PVA))) exists the metallo-organic compound (metal alkoxide) of surplus and hole to form the possibility that material (PVA) can form impurity less than above-mentioned scope.On the other hand, if greater than above-mentioned scope, existing, this mass ratio is difficult at positive active material surface whole metallizing organic compound (metal alkoxide) and is difficult in metallo-organic compound (metal alkoxide), disperse equably form the possibility that material is attached to the positive active material surface with the hole formation material of metallo-organic compound phase-splitting with the hole.
In addition, above-mentioned solvent changes based on the kind that the hole forms material, metallo-organic compound, positive active material etc., and be not particularly limited,, and can obtain predetermined colloidal sol as long as this dissolution with solvents hole forms material, metallo-organic compound, positive active material.The example of solvent comprises ethanol, acetylacetone,2,4-pentanedione, isopropyl alcohol, methyl alcohol etc.Especially, quote the example of ethanol as solvent.
Together with the technology of wherein adding among metallo-organic compound, hole formation material and positive active material and the colloidal sol preparation technology who reaches the scheduled time that under predetermined temperature, stirs the mixture, with previous materials add solvent method, material added the order of solvent, the condition that comprises temperature/mixing time etc., stirring means etc. all be not particularly limited, but can suitably select according to the condition of expectation, as long as can provide and then obtain the colloidal sol of the positive active material that is coated with colloidal sol of above-mentioned expectation.About among the colloidal sol preparation technology metallo-organic compound, hole being formed the order that material and positive active material add solvent, preferably, at first add metallo-organic compound, after stirring, add the hole and form material, stir again, add positive active material afterwards, stir once more.
Next filtering technique is described.A kind of like this technology of filtering technique in the sol-gel technology flow process shown in Figure 5, wherein, filter in aforementioned colloidal sol preparation technology, obtaining colloidal sol, with from forming the fine particle material separating liquid that material and positive active material are formed by the metallo-organic compound the colloidal sol, hole, so that obtain fine particle (hereinafter being sometimes referred to as filtration fraction).Filtering technique is not particularly limited, as long as the filtration fraction that this technology can obtain to be scheduled to.Can use the typical filter method.The example of filtering technique comprises a kind of like this method, wherein paper filter is arranged on the glass funnel, pours into the colloidal sol that obtains among the colloidal sol preparation technology, thereby by filter colloidal sol is filtered, and collects the filtration fraction that is retained on the filter.The example of filtering technique also comprises other method.
Next gelation technology is described.Gelation technology in the sol-gel technology flow process shown in Figure 5 is a kind of like this technology, wherein, use the filtration fraction that obtains after the filtering technique, by on the positive active material surface, forming the positive active material that the gel coating film obtains to be coated with gel, in described gel coating film, disperse equably and be attached with metallo-organic compound and form material with the hole of metallo-organic compound phase-splitting.This technology is not particularly limited, and can use common method as gelation technology, as long as can obtain the positive active material that is coated with gel of above-mentioned expectation.The example of gelation technology comprises a kind of like this method, wherein, under predetermined temperature, will obtain the filtration fraction drying and reach the scheduled time by filtering technique, and with evaporation with remove unnecessary solvent etc. and dewater-condensation, etc.
In gelation technology, predetermined temperature forms variations such as the kind of material, metal-organic kind, solvent types based on kind, the hole of positive active material, and be not particularly limited, as long as this temperature allows to carry out dehydrating condensation and therefore makes the filtration fraction gelation that obtains by filtering technique.For example, at positive active material is that cobalt acid lithium, hole formation material are that polyvinyl alcohol (PVA), metallo-organic compound are that metal alkoxide and solvent are under the situation of ethanol series solvent, preferably, predetermined temperature is in 0 to 100 ℃ scope, especially in 25 to 50 ℃ scope.If the temperature during the dehydrating condensation is lower than above-mentioned scope, there is the possibility that is difficult to carry out gelation.On the other hand, if temperature is higher than described scope, there is the possibility of gel decomposition.
In addition, when positive active material in gelation technology is that to form material be that polyvinyl alcohol (PVA), metallo-organic compound are metal alkoxide and solvent when being the ethanol series solvent cobalt acid lithium, hole, the scheduled time is usually in 0.1 to 5 hour scope.
In gelation technology, under predetermined temperature, carry out drying and reach the scheduled time to evaporate and to remove unnecessary solvent and cause that the atmosphere of dehydration-condensation is not particularly limited, as long as this atmosphere allows to form the gel coating film on the positive active material surface, in described gel coating film, disperse equably and be attached with metallo-organic compound and form material with the hole of metallo-organic compound phase-splitting.Usually, in atmosphere, carry out gelation technology.
Next sintering process of the present invention is described.Make in the flow process at the positive active material that is coated with metal oxide shown in Figure 4, sintering process of the present invention is a kind of like this technology, wherein, carry out sintering in aforementioned sol-gel technology, obtaining the gel coating film, form material and therefore on the positive active material surface, form coating of metal oxides to decompose and to remove the hole, in described coating of metal oxides, be formed uniformly porosely, allow lithium ion to move by described hole.This sintering process is not particularly limited, it can be common method, this sintering process forms material and on the positive active material surface, forms coating of metal oxides as long as can decompose and remove the hole, in described coating of metal oxides, be formed uniformly porosely, allow lithium ion to move by described hole.Particularly, the example of sintering process comprises a kind of like this method, wherein in predetermined atmosphere and under predetermined temperature, the positive active material that is coated with gel is carried out sintering reach the scheduled time.The example of this sintering process also comprises other method etc.
The predetermined temperature that is used for the sintering of aforementioned technology forms variations such as the kind of material, metal-organic kind based on the kind of the positive active material that uses, hole in being coated with the positive active material of gel.Sintering temperature is not particularly limited, and forms material and form coating of metal oxides on the positive active material surface as long as the hole can be decomposed and remove to this temperature, is formed uniformly porosely in described coating of metal oxides, moves by described hole permission lithium ion.For example, be that cobalt acid lithium, hole formation material are that polyvinyl alcohol (PVA), metallo-organic compound are under the situation of metal alkoxide at positive active material, sintering temperature is usually in 100 to 800 ℃ scope.
For example, positive active material is that cobalt acid lithium, hole formation material are that polyvinyl alcohol (PVA), metallo-organic compound are under the situation of metal alkoxide in sintering process, and the scheduled time of sintering is usually in 5 to 500 hours scope.
In sintering process, under predetermined temperature the positive active material execution drying that is coated with gel being reached the atmosphere of the scheduled time is not particularly limited, as long as this atmosphere allows to decompose and removes the hole and forms material and form coating of metal oxides on the positive active material surface, in described coating of metal oxides, be formed uniformly porosely, allow lithium ion to move by described hole.Usually, in atmosphere or oxygen atmosphere, carry out sintering.
Next describe the embodiment of the manufacture method that is used for lithium secondary battery of the present invention in detail.Fig. 6 illustrates the example (lithium secondary battery making flow chart) of the flow process of the manufacture method that is used for lithium secondary battery of the present invention.As shown in Figure 6, be used for the manufacture method of lithium secondary battery of the present invention, carry out the anode electrode system and make technology, wherein, the positive active material that is coated with metal oxide that utilization obtains in the above-mentioned manufacture method of the positive active material that is used for being coated with metal oxide, on positive electrode collector, make anodal layer, so that make the positive electrical polar body that comprises anodal layer and positive electrode collector.Then, carry out the negative electrode system and make technology, wherein, on negative electrode collector, make negative electrode layer so that make the negative electricity polar body that comprises negative electrode layer and negative electrode collector.Afterwards, arrange positive electrical polar body and negative electricity polar body, between anodal layer and negative electrode layer, predetermined dividing plate to be set.Then, carry out the battery packaging technology, wherein, the predetermined electrolyte of filling in anodal layer, negative electrode layer and dividing plate inserts dividing plate in the battery container etc., so that the formation battery by the sub-component of positive electrical polar body and the clamping of negative electricity polar body afterwards.Thereby, can obtain the lithium secondary battery of above-mentioned expectation.By the way, the anode electrode system is made technology and negative electrode system and is made technology and can carry out simultaneously, perhaps carries out the anode electrode system and make technology after the negative electrode system is made technology.
According to the present invention, because the above-mentioned manufacture method of the positive active material by being used to be coated with metal oxide obtains to improve cycle characteristics and suppresses the positive active material that is coated with metal oxide that output characteristic reduces, so the positive active material that is coated with metal oxide by use can obtain to improve cycle characteristics and suppress the lithium secondary battery that output characteristic reduces.
The manufacture method that is used for lithium secondary battery of the present invention is not particularly limited, and it can also comprise other technology, makes technology as long as this manufacture method comprises the anode electrode system at least.Hereinafter describe each technology of the manufacture method that is used for lithium secondary battery of the present invention in detail.
Anode electrode system of the present invention is a kind of like this technology as technology, wherein, the positive active material that is coated with metal oxide that the manufacture method of the positive active material of utilization by being used to be coated with metal oxide obtains is made anodal layer, and on anodal layer, arrange positive electrode collector, so that make the positive electrical polar body that comprises anodal layer and positive electrode collector.Particularly, this method is not particularly limited, it can be common method, as long as this method can be made the positive electrical polar body, wherein, on positive electrode collector, made anodal layer with positive active material that is coated with metal oxide that the above-mentioned manufacture method at the positive active material that is used for being coated with metal oxide obtains.For example, after obtaining solution by the predetermined attachment material of dissolving in predetermined solvent, positive active material that is coated with metal oxide and predetermined conductive agent that the manufacture method of positive active material that will be by being used for being coated with metal oxide obtains are introduced above-mentioned solvent, mix described solution afterwards equably to make anodal layer with sticking with paste (paste).Anodal layer is layed onto on the side of being scheduled to positive electrode collector with muddled.After drying, suppress etc., positive electrode collector is cut into preliminary dimension etc., thereby make the positive electrical polar body.Then, this positive electrical polar body is arranged on the side of dividing plate.The method can be made technology as the anode electrode system, and other method etc. also can be used as the anode electrode system and makes technology.
Positive active material, attachment material, conductive agent, positive electrode collector and dividing plate that is coated with metal oxide and above-mentioned identical when illustrating in conjunction with lithium secondary battery are save their explanation at this.In addition, the solvent of doing to use in the technology in the anode electrode system is not particularly limited, as long as this solvent allows to obtain the anodal layer of above-mentioned expectation with sticking with paste.The example of this solvent comprises N-methyl pyrrolidone etc.
The manufacture method that is used for lithium secondary battery of the present invention is not particularly limited, and makes technology as long as this method comprises the anode electrode system at least.Usually, except the anode electrode system is made technology, this method also comprises: the negative electrode system of making the negative electricity polar body that comprises negative electrode layer and negative electrode collector is made technology, with the battery packaging technology, wherein, arrange positive electrical polar body and negative electricity polar body, between anodal layer and negative electrode layer, predetermined dividing plate to be set, the predetermined electrolyte of filling in anodal layer, negative electrode layer and dividing plate then, afterwards dividing plate is inserted in the battery container etc., so that form battery by the sub-component of positive electrical polar body and the clamping of negative electricity polar body.The technology that these technologies are carried out when general lithium secondary battery is provided is identical, saves their explanation at this.And, comprise that the lithium secondary battery that is obtained of electrolyte etc. is identical with above-mentioned " lithium secondary battery ", thereby save its explanation.
The invention is not restricted to the foregoing description.The foregoing description only is illustrative, and the technology of the present invention scope comprises any structure that has with the essentially identical structure of the described technological thought of claims and identical or similar operations and effect etc.
Further specifically describe the present invention below in conjunction with example.
In example of the present invention (hereafter is an example), with the Zr (OC of 10g
4H
9)
4Be dissolved in the ethanol of 100g, at room temperature stirred then 3 hours.Afterwards, the polyvinyl alcohol of dissolving 10g stirred 7 hours, to obtain colloidal sol.Afterwards, the cobalt acid lithium powder with 100g adds in the colloidal sol.After stirring 5 minutes, filter.The filtration fraction that will obtain by filtration at room temperature dry 1 hour afterwards 400 ℃ of following sintering 10 hours, (is coated with ZrO so that obtain to be coated with the positive active material of metal oxide
2Cobalt acid lithium (LiCoO
2)).
Then, with the ZrO that is coated with that 90g obtained
2Cobalt acid lithium (LiCoO
2) powder and 10g add in the N-methyl pyrrolidone solution of 125mL as solvent as the carbon black of electric conducting material, wherein, has been dissolved with the Kynoar (PVDF) of 5g as attachment material in the N-methyl pyrrolidone solution as solvent.The mixture that mixes formation is up to even mixing.Thereby, make anodal layer with sticking with paste.Anodal layer is overlayed on the side of the thick Al collector body of 15 μ m with muddled, dry then, make the positive electrical polar body thus.Per unit area electrode amount is 6mg/cm
2Suppressing this positive electrical polar body, is that the anodal layer of 45 μ m is with sticking with paste and density is 1.6g/cm to obtain thickness
3Anodal layer with sticking with paste.Afterwards, cutting this positive electrical polar body, is the positive electrical polar body that cuts of φ 16 to obtain diameter.
92.5g is added in the N-methyl pyrrolidone solution of 125mL as solvent as the powdered graphite of negative electrode active material, be dissolved with the Kynoar (PVDF) of 7.5g in the N-methyl pyrrolidone solution as solvent as attachment material.The mixture that mixes formation is up to even mixing.Thereby, make negative electrode layer with sticking with paste.Negative electrode layer is layed onto on the side of the thick Cu collector body of 15 μ m with muddled, dry then, make the negative electricity polar body thus.Per unit area electrode amount is 4mg/cm
2Suppressing this negative electricity polar body, is that the negative electrode layer of 20 μ m is with sticking with paste and density is 1.2g/cm to obtain thickness
3Negative electrode layer with sticking with paste.Afterwards, cutting this negative electricity polar body, is the negative electricity polar body that cuts of φ 19 to obtain diameter.
Utilize above-mentioned positive pole, above-mentioned negative pole and, make CR2032 type coin shape battery (lithium battery) as the PP system-porous matter dividing plate of aforementioned barriers.Used electrolyte solution is by will be as the lithium hexafluoro phosphate (LiPF of supporting electrolyte
6) be dissolved in concentration be 1mol/L pass through mix the solution that obtains in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) formation with 3: 7 volume ratio.
Example 1 as a comparison, makes coin shape battery in the mode identical with example, except the positive active material that is coated with metal oxide does not add polyvinyl alcohol and makes.
In comparative example 2, make coin shape battery in the mode identical with example, except as positive active material, the positive active material that uses uncoated cobalt acid lithium to replace being coated with metal oxide (is coated with ZrO
2Cobalt acid lithium (LiCoO
2)).
The coin shape battery that utilization obtains in example, comparative example 1 and comparative example 2 is carried out the test of relevant lithium ion impedance and cycle characteristics.By with 3.0 to 4.0V aging (processing) afterwards, SOC is adjusted to 60%, under 25 ℃, utilize the impedance of AC impedance measurement lithium ion.Frequency setting is 10mHz to 100Hz.In addition, as cycle characteristics, after measuring the lithium ion impedance, 3.0 to 4.1V, under 2C and 60 ℃, measure the discharge capability sustainment rates by 500 circulations.In addition, in order to show ZrO by the positive active material surface
2The coating rate of realizing is measured the Co/Zr ratio by the positive active material that uses in example, comparative example 1 and the comparative example 2 is carried out quantitative analysis.Gained the results are shown in the table 1.
[table 1]
| Cycle characteristics | The lithium ion impedance | Co/Zr (XPS analysis) | |
| Example | ??92％ | ??4.0Ω | ??50/50 |
| Comparative example 1 | ??95％ | ??8.0Ω | Noise level/100 |
| Comparative example 2 | ??70％ | ??4.0Ω | 100/ noise level |
As shown in table 1, the cycle characteristics in the example is 92%, and the cycle characteristics in the comparative example 1 is 95%, and the cycle characteristics in the comparative example 2 is 70%.Therefore, the cycle characteristics of example and comparative example 1 are basic identical, and good than example 2 frequently.In addition, the lithium ion impedance in the example is 4.0 Ω, and the impedance in the comparative example 1 is 8.0 Ω, and the impedance in the comparative example 2 is 4.0 Ω.Thereby lithium ion impedance and comparative example 2 in the example are basic identical, and good than example 1 frequently.
The Co/Zr that obtains by XPS analysis is 50/50 in example, is noise level/100 in comparative example 1, is 100/ noise level in comparative example 2.These results' demonstrations, in example, positive active material cobalt acid lithium (LiCoO
2) the whole ZrO that is coated with in surface
2, and at ZrO
2Exist equably in the coating from cobalt acid lithium (LiCoO
2) surface is communicated to ZrO
2The hole of coating surface.In addition, can also demonstrate, in comparative example 1, positive active material cobalt acid lithium (LiCoO
2) the whole ZrO that is coated with in surface
2, but there is not the hole.In addition, can also demonstrate, in comparative example 2, positive active material cobalt acid lithium (LiCoO
2) surface do not have whole coating ZrO
2
Can also obtain such conclusion from these results, that is, and owing to the acid of positive active material cobalt in example lithium (LiCoO
2) the whole ZrO that is coated with in surface
2So that positive active material cobalt acid lithium surface is by whole coating, therefore positive active material since the deterioration that causes with reaction such as electrolyte solution suppressed effectively, and therefore in example cycle characteristics be improved to comparative example 1 in essentially identical level, positive active material cobalt acid lithium (LiCoO in comparative example 1
2) the whole ZrO that is coated with in surface
2, but there is not the hole.And, because in example at ZrO
2Exist equably in the coating from positive active material cobalt acid lithium (LiCoO
2) surface is communicated to ZrO
2The hole of coating surface allows lithium ion to move by described hole, thus lithium ion can in intercommunicating pore, move, and in example owing to being coated with ZrO
2The lithium ion impedance increase that causes and output characteristic reduce be suppressed to comparative example 2 in essentially identical degree, positive active material cobalt acid lithium (LiCoO in comparative example 2
2) surface do not have whole coating ZrO
2
Claims (16)
1. positive active material that is coated with metal oxide, it has the coating of metal oxides with the surperficial whole coating of positive active material, it is characterized in that, whole surface is provided with the hole that is communicated to the surface of described coating of metal oxides from the described surface of described positive active material in the described coating of metal oxides, allows lithium ion to move by described hole.
2. the positive active material that is coated with metal oxide according to claim 1, wherein, described hole is arranged in the described coating of metal oxides equably.
3. the positive active material that is coated with metal oxide according to claim 1 and 2, wherein, the density that is formed on the described hole in the described coating of metal oxides is at 10 to 1000000/μ m
2Scope in.
4. the positive active material that is coated with metal oxide according to claim 3, wherein, the density that is formed on the described hole in the described coating of metal oxides is at 1000 to 10000/μ m
2Scope in.
5. according to each described positive active material that is coated with metal oxide among the claim 1-4, wherein, the size in described hole is in the scope of 0.1nm to 100nm.
6. the positive active material that is coated with metal oxide according to claim 5, wherein, the size in described hole is in the scope of 1nm to 10nm.
7. according to each described positive active material that is coated with metal oxide among the claim 1-6, wherein, the film thickness of described coating of metal oxides is in the scope of 1nm to 1000nm.
8. the positive active material that is coated with metal oxide according to claim 7, wherein, the film thickness of described coating of metal oxides is in the scope of 10nm to 100nm.
9. a use is according to each described lithium secondary battery that is coated with the positive active material of metal oxide among the claim 1-8.
10. manufacture method that is used to be coated with the positive active material of metal oxide comprises:
Carry out sol-gel technology, described sol-gel technology forms the gel coating film on the surface of positive active material, in described gel coating film, disperse and be attached with metallo-organic compound and with the hole formation material of described metallo-organic compound phase-splitting, and
Carry out sintering process, the described gel coating film that obtains in described sol-gel technology by sintering decomposes and removes described hole and forms material, with on the described surface of described positive active material, form coating of metal oxides, in described coating of metal oxides, on the whole described surface of described positive active material, form the hole, allow lithium ion to move by described hole.
11. manufacture method according to claim 10, wherein, form in described sol-gel technology that wherein said metallo-organic compound and described hole form that material is evenly dispersed and the described gel coat film that adheres to and be formed uniformly described hole in the described coating of metal oxides in described sol-gel technology by the described gel coat film that sintering obtains.
12. according to claim 10 or 11 described manufacture methods, wherein, described metallo-organic compound is a metal alkoxide.
13. according to each described manufacture method among the claim 10-12, wherein, it is polyvinyl alcohol that described hole forms material.
14. manufacture method according to claim 13, wherein, the number-average molecular weight of described polyvinyl alcohol is in 100 to 10000 scope.
15. manufacture method according to claim 14, wherein, the number-average molecular weight of described polyvinyl alcohol is in 500 to 2000 scope.
16. a manufacture method that is used for lithium secondary battery comprises
Use is made the positive electrical polar body by the positive active material that is coated with metal oxide that obtains according to each described manufacture method among the claim 10-15.
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| JP2007228891A JP2009064576A (en) | 2007-09-04 | 2007-09-04 | Positive electrode active material and lithium secondary battery |
| JP228891/2007 | 2007-09-04 | ||
| PCT/IB2008/002953 WO2009031036A2 (en) | 2007-09-04 | 2008-09-04 | Metal oxide-coated positive electrode active material, lithium secondary battery, and manufacture method therefor |
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| JP2004175609A (en) * | 2002-11-26 | 2004-06-24 | Ind Technol Res Inst | Lithium cobaltate used for positive electrode of lithium ion battery, its manufacturing process and lithium ion battery |
| JP2006156032A (en) * | 2004-11-26 | 2006-06-15 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method |
| JP2006216374A (en) * | 2005-02-03 | 2006-08-17 | Sony Corp | Negative electrode material and battery using it |
| KR100759556B1 (en) * | 2005-10-17 | 2007-09-18 | 삼성에스디아이 주식회사 | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
-
2007
- 2007-09-04 JP JP2007228891A patent/JP2009064576A/en active Pending
-
2008
- 2008-09-04 KR KR1020107004751A patent/KR20100051705A/en not_active Application Discontinuation
- 2008-09-04 WO PCT/IB2008/002953 patent/WO2009031036A2/en active Application Filing
- 2008-09-04 CN CN200880105510A patent/CN101796671A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104025341A (en) * | 2011-12-30 | 2014-09-03 | 三星精密化学株式会社 | Cathode Active Material For Lithium Secondary Battery, Manufacturing Method Thereof, And Lithium Secondary Battery Including Same |
| CN104025341B (en) * | 2011-12-30 | 2017-05-10 | 三星Sdi株式会社 | Cathode Active Material For Lithium Secondary Battery, Manufacturing Method Thereof, And Lithium Secondary Battery Including Same |
| CN104364942A (en) * | 2012-06-29 | 2015-02-18 | 丰田自动车株式会社 | Composite active material, solid-state battery and method for producing composite active material |
| US9887417B2 (en) | 2012-06-29 | 2018-02-06 | Toyota Jidosha Kabushiki Kaisha | Composite active material, solid state battery and method for producing composite active material |
| CN106716701A (en) * | 2014-09-26 | 2017-05-24 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN105244488A (en) * | 2015-11-16 | 2016-01-13 | 湖南杉杉能源科技股份有限公司 | Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material |
| CN113346047A (en) * | 2021-06-04 | 2021-09-03 | 江西安驰新能源科技有限公司 | Low-temperature lithium ion battery positive pole piece and preparation method thereof, and lithium ion battery |
| WO2023207249A1 (en) * | 2022-04-24 | 2023-11-02 | 广东邦普循环科技有限公司 | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
| GB2625624A (en) * | 2022-04-24 | 2024-06-26 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100051705A (en) | 2010-05-17 |
| WO2009031036A2 (en) | 2009-03-12 |
| JP2009064576A (en) | 2009-03-26 |
| WO2009031036A3 (en) | 2009-05-28 |
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