CN107305946A - Composite transition metal oxide system precursor, its manufacture method and anode active material - Google Patents
Composite transition metal oxide system precursor, its manufacture method and anode active material Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of composite transition metal oxide system precursor, its manufacture method and anode active material, composite transition metal oxide system precursor is the composite transition metal oxide comprising nickel (Ni) and heterogeneous transition group metal, and crystal structure has the structure that cubic system or cubic system and spinelle mix.By the present invention in that with the excellent composite transition metal oxide system precursor of structural stability, not only improve keeping and the operability of precursor phases, the anode active material using above-mentioned precursor is readily synthesized, and the anode active material of long-term reliability and the excellent secondary cell of electrochemical properties can be provided.
Description
Technical field
The present invention relates to constitutionally stable composite transition metal oxide system precursor and its manufacture method, include above-mentioned precursor
And the excellent secondary cell anode active material of long-term reliability.
Background technology
In recent years, actual conditions are, as the miniaturization of electronic equipment is, it is necessary to the secondary cell of high power capacity, with NI-G electricity
Pond, the Ni-MH battery lithium secondary battery high compared to energy density are particularly subject to concern.
It is main to use the (LiCoO containing lithium and cobalt oxides as the anode active material of lithium secondary battery2), in addition,
Use the LiMnO of layered crystal structure2, spinel crystal structure LiMn2O4Aoxidized Deng lithium-magnesium containing oxide and as nickel containing lithium
The LiNiO of thing2。
On the other hand, above-mentioned lithium composite transition metal oxide system anode active material typically utilizes hexagonal crystal system
(Hexagonal) the composite transition metal hydroxide (Hydroxide) of crystal structure is precursor and lithium precursor and by solid phase
Synthetic method is manufactured.Composite transition metal hydroxide system precursor with such hexagonal crystal structure is in an atmosphere not
It is stable, therefore can make locally to occur to aoxidize and cause undesirable surface to be reacted.Thus manufacture mole in stoichiometry with lithium
Than unmatched anode active material, so as to produce the problem of capacity for the battery for possessing it, life characteristic and reliability are reduced.
Particularly, nickel (Ni) content high nickelic (High-Ni) is that anode active material can hold because of the sensitive reactivity with moisture
Easily aoxidize, therefore there are the following problems：Not only be difficult to take care of in an atmosphere, and because above-mentioned surface reaction become active and
Making the electrochemistry physical property and reliability properties of final anode active material substantially reduces.Therefore, actual conditions are, in the urgent need to opening
Hair Stability Analysis of Structures, easily keeping and the long-term reliability of lithium secondary battery and the new composition of chemical property can be improved
Anode active material.
The content of the invention
Problem to be solved
The present invention proposes that its object is to have there is provided one kind in order to solve the problems, such as conventional art as described above
The cubic system (Cubic) of configurational stabilisation or exist spinel type compound cubic system crystal structure compound transition gold
Belong to oxide system's precursor and its manufacture method, so that instead of hexagonal crystal system composite transition metal hydroxide unstable in air
It is the use of precursor.
In addition, another object of the present invention is to there is provided by above-mentioned composite transition metal oxide system precursor and lithium precursor
Manufacture and the electrochemical properties of battery and the secondary cell anode active material of long-term reliability can be played.
The method for solving problem
To achieve these goals, the present invention provides the composite transition metal oxide that a kind of crystal structure is cubic system
It is precursor, it is the composite transition metal oxide comprising nickel (Ni) and heterogeneous transition group metal, is utilizing the Alpha-ray X-rays of CuK
In difraction spectrum, with angle of diffraction (2 θ) be 37~39 °, 42~44 °, 62~64 °, 75~77 ° and 78~80 ° when occur
5 peaks, and crystal structure be cubic system.
According to preferred one of the present invention, above-mentioned precursor can be further contained in the angle of diffraction of X-ray diffraction spectra
3 peaks that degree (2 θ) occurs when being 30~32 °, 36~38 ° and 58~60 °, and cubic system and spinelle (Spinel) crystal
Structure mixes.
In the present invention, above-mentioned anode active material precursor is preferably represented by following chemical formula 1.
[chemical formula 1]
NiaCobM’cOx
In above-mentioned formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 races member
One or more of group of element, transition metal and rare earth element composition,
1≤x≤1.5,0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
In above-mentioned chemical formula 1, M ' is preferably selected from by Al, Mn, Zr, W, Ti, Mg, Sr, Ba, Ce, Hf, F, P, S, La and Y
One or more of group of composition.
In the present invention, above-mentioned precursor can be the offspring of primary particle or multiple primary particle aggegations.Its
In, above-mentioned primary particle can be the sheet (flake) or needle-like (Niddle) shape that average grain diameter is 0.01~0.8 μ m
State.In addition, the average grain diameter (D50) of above-mentioned offspring is 3~30 μ ms, there may be many stomata knots on surface or inside
Structure.
Also, the present invention provides the anode manufactured comprising above-mentioned composite transition metal oxide system precursor and lithium precursor and lived
Property material.
In the present invention, above-mentioned anode active material nickel (Ni) content preferably in whole transition metal is more than 60%.
Further, the present invention provides the manufacture method of above-mentioned composite transition metal oxide system precursor.
More specifically, above-mentioned manufacture method can be included the composite transition metal hydrogen-oxygen represented by following chemical formula 2
The step of compound carries out heat treatment in 1~12 hour under air atmosphere or oxygen atmosphere with 700~1100 DEG C of temperature.
[chemical formula 2]
NiaCobM’c(OH)2
In above-mentioned formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 races member
One or more of group of element, transition metal and rare earth element composition,
0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
Invention effect
In the present invention, there is the cubic system of Spinel by using the stable cubic system of crystal structure or on surface
Composite transition metal oxide system precursor come replace in the past be used as anode active material precursor hexagonal crystal system composite transition metal
Hydroxide system precursor, using the teaching of the invention it is possible to provide keeping and operability are improved, and utilize the synthesis of the anode active material of above-mentioned precursor
Easily, the anode active material of long-term reliability and the excellent secondary cell of electrochemical properties.
Brief description of the drawings
Fig. 1 is the SEM image of the particle shape of composite transition metal oxide system precursor for representing to manufacture in embodiment 1.
Fig. 2 is that the SEM for the particle shape for representing the composite transition metal hydroxide system precursor manufactured in comparative example 1 schemes
Picture.
Fig. 3 is X-ray diffraction analysis (XRD) result for the composite transition metal hydroxide system precursor for representing comparative example 1
Chart.
Fig. 4 is the figure of X-ray diffraction analysis (XRD) result of anode active material precursor for representing to manufacture in embodiment 1
Table.
Fig. 5 is the X-ray diffraction analysis (XRD) for comparing the composite transition metal precursor manufactured in comparative example 1 and embodiment 1
As a result chart.
Fig. 6 is to represent that the life-span for possessing the lithium secondary battery of the anode active material manufactured in comparative example 1 and embodiment 1 is special
The chart of property.
Embodiment
Hereinafter, the present invention is described in detail.
It is a feature of the present invention that being stood as anode active material precursor (precursor) using crystal structure is stable
Prismatic crystal system or the cubic system composite transition metal oxide system precursor that there is Spinel on surface replace conventional hexagonal crystal system
Composite transition metal hydroxide system precursor.
More specifically, in the present invention, the hydroxide system manufactured in the past by being co-precipitated process is made to be combined transition gold
Belong to precursor via heat treatment step, know from experience vertical with configurational stabilisation before the composite transition metal manufactured via such process
Prismatic crystal system or the cubic system crystal structure that there is Spinel on surface.Therefore, keeping is just made since precursor phases and is grasped
Improved as property, the anode active material using above-mentioned precursor can be easily synthesized.
Especially in the present invention, due to can manufacture to repeatability the sun being optimized in stoichiometry with the mol ratio of lithium
Pole active material, the particularly high nickelic system's active material of reactivity, possess the anode active material therefore, it is possible to significantly improve
Battery capacity, life characteristic and long-term reliability.
<Composite transition metal oxide system precursor and its manufacture method>
Answering comprising nickel (Ni) and heterogeneous transition group metal is used as according to the composite transition metal oxide system precursor of the present invention
Close transition metal oxide, it is characterised in that with crystal structure be cubic system or above-mentioned cubic system and spinelle knot
The structure that structure mixes.
There are following two kinds of forms on X-ray diffraction spectra (XRD) in above-mentioned composite transition metal oxide system precursor
Specific diffraction maximum, it embodies the crystal structure of above-mentioned precursor.
As according to the first embodiment of the invention, above-mentioned composite transition metal oxide system precursor is utilizing Cu-K α
It is 37~39 °, 42~44 °, 62~64 °, 75~77 ° to exist simultaneously in the X-ray diffraction spectra of ray in angle of diffraction (2 θ)
5 diffraction maximums occurred during with 78~80 °.It means that the crystal structure of above-mentioned composite transition metal oxide system precursor is
Cubic system.
In addition, as second method, above-mentioned composite transition metal oxide system precursor is spread out using the Alpha-ray X-rays of CuK
Penetrate in spectrum and go out while existing when angle of diffraction (2 θ) is 37~39 °, 42~44 °, 62~64 °, 75~77 ° and 78~80 °
Existing 5 from cubic system peak and coming from of occurring when angle of diffraction (2 θ) is 30~32 °, 36~38 ° and 58~60 °
3 peaks of spinelle.It means that the crystal structure of above-mentioned composite transition metal oxide system precursor is that cubic system and point are brilliant
The structure that stone mixes.
In the present invention, the ratio that above-mentioned cubic system and spinel structure mix can be by changing compound transition
Metal oxide system precursor is [for example, NiaCobM’cOx] composition, such as the elemental ratio of Ni, Co, Mn adjusts.For example, such as
Co or Mn ratio increase in really above-mentioned precursor, then can be because forming the Co with Spinel3O4Or Mn3O4Material and make sharp crystalline substance
The ratio increase of stone structure.Here, the mixing ratio of above-mentioned cubic crystal structure and spinel structure can be 100:1~20 weight
Than preferably spinel structure is less than 10%.
Preferably represented according to the anode active material precursor of the present invention by following chemical formula 1.
[chemical formula 1]
NiaCobM’cOx
In above-mentioned formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 races member
One or more of group of element, transition metal and rare earth element composition,
1≤x≤1.5,0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
In above-mentioned chemical formula 1, a, b and c represent that mole % of each element in compound, x represent oxygen rate in compound.
Especially in the anode active material of the present invention, a be nickel (Ni) content can for more than 0.6, preferably 0.6~
0.9 scope, more preferably 0.7~0.9 scope.In addition, it can be more than 1, preferably 1~1.5 that x, which is oxygen rate,
Scope.In the case where meeting above-mentioned a and x scope, the composite transition metal with structural stability can be easily manufactured
Oxide system precursor, particularly nickelic system's anode active material, so as to show manufacture anode active material it is excellent
Electrochemistry physical property (long-term reliability, high initial capacity and long-life characteristics).
In the present invention, though by high nickel-based compound oxide is replaced a small amount of dissimilar metal, metalloid or other
The M ' of anion component etc. and Ni contents is increased to more than 60%, can also continue to maintain the structure of final anode active material
Stability and electrochemical properties.
According to the present invention preferably one, above-mentioned M ' can be selected from by Al, Mn, Zr, W, Ti, Mg, Sr, Ba, Ce, Hf,
One or more of group of F, P, S, La and Y composition.
In the present invention, above-mentioned composite transition metal oxide system precursor can be that primary particle or multiple primary particles are solidifying
The offspring of collection.Now, above-mentioned primary particle can be the sheet or needle-like that average grain diameter is 0.01~0.8 μ m
Form, can be in its surface and/or the internal structure that many air hole structures are distributed with.In addition, above-mentioned primary particle aggegation is formed
Offspring can be average grain diameter (D50) be 3~30 μ ms spherical morphology, but not by this especially limit.X-ray is spread out
Penetrate in analysis, the lattice constant of above-mentioned precursor has a=b=c value.
In the present invention, above-mentioned composite transition metal oxide system precursor because surface is formed with many air hole structures, therefore
The effect of increase specific surface area can be shown.For example, the specific surface area of the above-mentioned precursor determined according to nitrogen adsorption BET method can
To be 5~80m2/ g scope, preferably can be 5~50m2/g。
In addition, the tap density (tap density) of above-mentioned composite transition metal oxide system precursor powder is preferably
More than 2.0g/cc, more preferably more than 2.1g/cc.
Hereinafter, the manufacture method for the anode active material precursor according to the present invention is illustrated.But, it is not limited only to
Following manufacture methods, can be as desired by the step of changing each operation or selectivity is used with and implemented.
The preferred one embodiment for manufacturing above-mentioned anode active material precursor is enumerated, can be by by composite transition metal
Hydroxide is under air atmosphere so that 700~1100 DEG C of temperature carries out heat treatment in 1~12 hour and manufactures.
Now, as long as composite transition metal hydroxide system's precursor includes nickel and for hydroxide form with high content, just
It is not particularly limited.For example, can be indicated as following chemical formula 2.
[chemical formula 2]
NiaCobM’c(OH)2
In above-mentioned formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 races member
One or more of group of element, transition metal and rare earth element composition,
0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
According to preferred one of the present invention, above-mentioned M ' can be selected from by Al, Mn, Zr, W, Ti, Mg, Sr, Ba, Ce,
One or more of group of Hf, F, P, S, La and Y composition.
In the present invention, above-mentioned heat-treating atmosphere is not particularly limited, for example, it may be air atmosphere or oxygen atmosphere.This
Outside, heat treatment condition is not particularly limited, for example, can carry out being heat-treated for 1~12 hour with 700~1100 DEG C of scope, it is excellent
Elect 700~900 DEG C of scope as.
<Anode active material>
It is that the lithium manufactured by above-mentioned composite transition metal oxide system precursor is combined according to the anode active material of the present invention
Transition metal oxide.
More specifically, above-mentioned anode active material can be represented by following chemical formula 3.
[chemical formula 3]
LiyNiaCobM’cO2
In above-mentioned chemical formula 3,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 races member
One or more of group of element, transition metal and rare earth element composition,
0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1, and 0.9≤y≤1.3.
According to preferred one of the present invention, above-mentioned M ' can be selected from by Al, Mn, Zr, W, Ti, Mg, Sr, Ba, Ce,
One or more of group of Hf, F, P, S, La and Y composition.
In the present invention, above-mentioned anode active material can be that nickel (Ni) content is more than 60% in whole transition metal
The active material of rich nickel (Ni-rich) system, preferably 60~99% scope, more preferably 70~90%.
As long as the average grain diameter of above-mentioned anode active material can act as the normal ranges of active material just without special
Limitation.For example, it may be the scope of 5~30 μm of scope, preferably 5~20 μm.
The anode active material of the present invention can be manufactured according to conventional method well known in the art, for example, can pass through
Dry process, damp process and are used to manufacture.
One of the method for manufacturing above-mentioned anode active material is enumerated, can be by the way that above-mentioned oxide system and hydrogen will be included
The solid phase reaction that is heat-treated is manufactured after conductive anodic active substance precursors and lithium the precursor mixing of oxide system.
Here, on lithium precursor, being just not particularly limited as long as can act as supply source comprising lithium.It is preferred that can be
LiOH、Li2CO3Or their mixture.
In addition, the blending ratio of conductive anodic active substance precursors and lithium precursor can be with conventional model known in the art
Enclose it is interior suitably adjusted, for example, can be 1:0.95~1.15 weight than scope.
As described above, by being mixed anode active material precursor and lithium precursor and implementing heat treatment, can be because of crystal structure
Interior displacement has lithium and forms lithium composite transition metal oxide.
Now, heat treatment condition is not particularly limited, for example, it is preferable to implement 0.5 under 700~1000 DEG C of atmospheric conditions
~10 hours.
As needed, secondary heat treatment process can be carried out afterwards or further comprises being classified process.
The anode active material manufactured in the present invention is mainly used as secondary cell anode material, in addition, such as may be used
To be used in the various fields that above-mentioned composition can be applied.
<Anode>
The present invention provides above-mentioned secondary cell anode material and the lithium secondary battery comprising it.
Now, as necessary condition, anode material of the invention is comprised at least by above-mentioned composite transition metal oxide system
The anode active material of precursor manufacture.For example, above-mentioned anode active material can be directly used as anode active material, or it is mixed with
The anode mixture of above-mentioned anode active material and bonding agent, the anode mixture for further adding solvent and obtaining are pasted, further will
It is coated on the scope that anode formed by collector etc. falls within the anode material of the present invention.
Above-mentioned anode can be manufactured according to conventional method well known in the art, for example, can as needed by adhesive,
Conductive agent, dispersant and anode active material are mixed and stirred for and manufactured after slurry, and (coating) is in collector and compresses for coating, so
After be dried and manufacture.
Now, the electrode material such as decentralized medium, adhesive, conductive agent, collector can use routine well known in the art
Material, relative to anode active material, can be suitably used adhesive of 1~10 weight than scope, 1~30 weight compares scope
Conductive agent.
As the example for the conductive agent that can be used, there are native graphite, Delanium, carbon black, acetylene black system and ink west
Ketjen black, Vulcan XC-72, Super P (super P), coke class, the carbon of Ge Wan oil companies (Gulf Oil Company)
Nanotube, graphene or their more than one mixtures etc..
In addition, as the representative example of above-mentioned bonding agent, have polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVdF) or
Its copolymer, butadiene-styrene rubber (SBR), cellulose etc., as the representative example of dispersant, there is isopropanol, N- crassitudes
Ketone (NMP), acetone etc..
As long as the high metal of the collector electric conductivity of above-mentioned metal material, the gold that the paste of above-mentioned material can be easily bonded
Category, and without reactivity in the voltage range of battery, it is possible to use any one metal.For example, having aluminium, copper or stainless
Net (mesh), paper tinsel (foil) of steel etc. etc..
<Lithium secondary battery>
Also, the present invention provides the secondary cell for including above-mentioned anode, preferably lithium secondary battery.
The lithium secondary battery of the present invention is utilized by the anode active matter of above-mentioned composite transition metal oxide system precursor manufacture
Matter, in addition, is not particularly limited, and can be manufactured according to conventional method well-known in the art.Such as, it can pass through
Barrier film is put between the anode and cathode and puts into nonaqueous electrolyte to manufacture.
Now, lithium secondary battery of the invention comprising negative electrode, anode, barrier film, electrolyte as battery inscape, its
In, on the inscape of the negative electrode in addition to above-mentioned anode, barrier film, electrolyte and other additives that may be needed, abide by
According to the key element of conventional lithium secondary battery well known in the art.
For example, above-mentioned negative electrode can use conventional cathode for lithium secondary battery active material well known in the art, it is used as
Nonrestrictive example, use can be embedded in/material of removal lithium embedded, such as, have lithium metal or lithium alloy, coke, Delanium,
Native graphite, organic high molecular compound comburant, carbon fiber, silicon systems, tin system etc..In addition, conductive agent, bonding agent and solvent with
The situation of above-mentioned anode is similarly used.
In addition, non-water system electrolyte includes electrolyte ingredient commonly known in the art, such as electrolytic salt and electrolyte
Solvent.
Above-mentioned electrolytic salt can be formed by the combination of (i) cation and (ii) anion, and (i) cation is selected from by Li+、Na+、K+The group of composition；(ii) anion is selected from by PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N
(CF3SO2)2 -、C(CF2SO2)3 -The group of composition, wherein, preferred lithium salts.As the specific example of lithium salts, there is LiClO4、
LiCF3SO3、LiPF6、LiBF4、LiAsF6With LiN (CF3SO2)2Deng.These electrolytic salts may be used alone or in combination two
More than kind.
Above-mentioned electrolyte solvent can use cyclic carbonate, linear carbonic ester, lactone, ether, ester, acetonitrile, lactams,
Ketone.
As the example of above-mentioned cyclic carbonate, there are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate
(BC), fluoroethylene carbonate (FEC) etc., as the example of above-mentioned linear carbonate, there is diethyl carbonate (DEC), carbonic acid two
Methyl esters (DMC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC) and methyl propyl carbonate (MPC) etc..It is used as the example of above-mentioned lactone
Son, there is gamma butyrolactone (GBL), as the example of above-mentioned ether, there is dibutyl ethers, tetrahydrofuran, 2- methyltetrahydrofurans, Isosorbide-5-Nitrae-twoAlkane, 1,2- dimethoxy-ethanes, 1,2- diethoxyethane etc..As the example of above-mentioned ester, there are methyl formate, formic acid second
Ester, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, butyl propionate, pivalic acid methyl esters
Deng.In addition, as above-mentioned lactams, having METHYLPYRROLIDONE (NMP) etc., as above-mentioned ketone, there is poly- methyl ethylene
Ketone.It is further possible to using the halogen derivatives of above-mentioned organic solvent, but not limited to this.Also, above-mentioned organic solvent also can
Use glycol dimethyl ether (glyme), diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether.These are organic
Solvent may be used alone or in combination two or more.
Above-mentioned barrier film can be unrestrictedly using playing a part of preventing the short circuit of two electrode interiors and be impregnated with electrolyte
Porous material.As its nonrestrictive example, there is polypropylene-based, polyethylene-based, polyolefin-based porous barrier film or above-mentioned
Composite porous barrier film of inorganic material etc. is with the addition of in porous separator.
Hereinafter, the present invention is illustrated by embodiment, but following embodiments and experimental example only illustrate one of the present invention
Mode, the scope of the present invention is not limited to following embodiments and experimental example.
[embodiment 1]
1-1. anode active materials precursor is manufactured
By Ni0.8Co0.1Mn0.1(OH)2Carry out being heat-treated for 3 hours at 800 DEG C, so as to manufacture the anode active matter of embodiment 1
Matter precursor.
1-2. anode active materials are manufactured
Use the anode active material precursor [Ni manufactured in above-described embodiment 1-10.8Co0.1Mn0.1O1.1] and be used as lithiumation
The LiOHH of compound2O, and with 1:After 1.02 mixed in molar ratio, carry out being heat-treated for 12 hours at 800 DEG C, so as to manufacture implementation
The anode active material of example 1.
1-3. anodes are manufactured
Using the parts by weight of anode active material 95 manufactured in embodiment 1-2 and the parts by weight of PvdF adhesives 2.5, it is used as conduction
The parts by weight of carbon black 2.5 of material are scattered in nmp solution and manufactured after slurry, are coated on Al collectors.Afterwards, roll-in is passed through
Machine rolls to manufacture anode.
1-4. lithium secondary batteries are manufactured
Using the anode manufactured in above-described embodiment 1-3, using lithium metal as to pole, and using by EC/EMC/DEC (40/
30/30, volume ratio) and 1M LiPF4The electrolyte manufacture button cell (coin cell) of composition.
[comparative example 1]
As hydroxide precursor and lithium precursor, respectively using Ni0.8Co0.1Mn0.1(OH)2Be used as lithium compound
LiOH·H2O, and with 1:After 1.02 mixed in molar ratio, carry out being heat-treated for 12 hours at 800 DEG C, so as to manufacture comparative example 1
Anode active material.
Using above-mentioned anode active material, in addition, implement in the same manner as above-described embodiment 1, manufacture the sun of comparative example 1
Pole and the lithium secondary battery for possessing it.
The particle shape evaluation of [experimental example 1] anode active material precursor
In order to confirm the form of the composite transition metal precursor manufactured in embodiment 1 and comparative example 1, SEM is implemented to them
Analysis.
Confirm the SEM image of the composite transition metal precursor of comparative example 1 and embodiment 1, as a result understand, embodiment 1 is answered
Equably it is made up of primary particle in the particle shape for closing transition metal oxide system precursor, the compound transition gold with comparative example 1
Category hydroxide system precursor is compared, and surface is formed with a large amount of stomatas (reference picture 1~2).
The X-ray diffraction analysis (XRD) of [experimental example 2] anode active material precursor
Implement XRD analysis using the composite transition metal oxide system precursor manufactured in embodiment 1.
XRD analysis equipment uses PANalytical X ' Rert PRO types, and x-ray source uses Cu κ α 8048eV.Now, spread out
The θ of firing angle degree 2 is measured with 10~90 degree of scope, and sweep speed is walked with 0.9sec/ to be implemented, and the results are shown in following Fig. 4.
Now, the composite transition metal hydroxide system precursor used in comparative example 1 is used as control group, the results are shown in following figures
3。
Experimental result shows that the composite transition metal hydroxide system precursor of comparative example 1 is only existed from hexagonal crystal system crystalline substance
The characteristic peak (reference picture 3) of body structure.
Compared to this, it is known that the anode active material precursor of embodiment 1 is significantly occurred in that from cubic system crystal knot
5 diffraction maximums [2 θ=37~39 °, 42~44 °, 62~64 °, 75~77 °, 78~80 °] of structure, and also exist brilliant from point
3 diffraction maximums [2 θ=30~32 °, 36~38 °, 58~60 °] (reference picture 4~5) of stone structure.
Chemical property evaluation-life characteristic the evaluation of [experimental example 3] secondary cell
Using the lithium secondary battery each manufactured in embodiment 1 and comparative example 1, chemical property is evaluated.
Now, in chemical property evaluation, in 3.0V~4.4V voltage regimes, 100 charge and discharges are implemented with 1C/1C circulations
Electrical testing, determines the conservation rate relative to initial capacity, the results are shown in table 1 below and Fig. 4.
Experimental result understands possess the embodiment of the anode by the precursor manufacture of cubic system composite transition metal oxide system
1 battery is compared with possessing the comparative example 1 of the anode manufactured using hexagonal crystal system composite transition metal hydroxide system precursor, tool
There are more excellent long-life characteristics (reference picture 6).
[table 1]
| Long-term reliability [100th, 1C/1C (%)] | |
| Comparative example 1 | 71.2 |
| Embodiment 1 | 76.5 |
Claims (10)
1. a kind of composite transition metal oxide system precursor, it is characterised in that be answering comprising nickel (Ni) and heterogeneous transition group metal
Close transition metal oxide,
Using in the Alpha-ray X-ray diffraction spectras of CuK, be 37~39 ° in the θ of angle of diffraction 2,42~44 °, 62~
5 peaks occurred at 64 °, 75~77 ° and 78~80 °,
And crystal structure is cubic system.
2. composite transition metal oxide system according to claim 1 precursor, it is characterised in that
The θ of angle of diffraction 2 that the precursor is further contained in X-ray diffraction spectra is 30~32 °, 36~38 ° and 58~60 °
When 3 peaks occurring,
And cubic system and spinel structure mix.
3. composite transition metal oxide system according to claim 1 precursor, it is characterised in that
The precursor is represented by following chemical formula 1：
[chemical formula 1]
NiaCobM’cOx
In the formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 race's elements, mistake
One or more of group of metal and rare earth element composition is crossed,
1≤x≤1.5,0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
4. composite transition metal oxide system according to claim 1 precursor, it is characterised in that
The M ' be in the group being made up of Al, Mn, Zr, W, Ti, Mg, Sr, Ba, Ce, Hf, F, P, S, La and Y it is a kind of with
On.
5. composite transition metal oxide system according to claim 1 precursor, it is characterised in that
The precursor is the offspring of primary particle or multiple primary particle aggegations.
6. composite transition metal oxide system according to claim 5 precursor, it is characterised in that
The primary particle is the sheet or acicular morphology that average grain diameter is 0.01~0.8 μ m,
The average grain diameter D50 of the offspring is 3~30 μ ms.
7. composite transition metal oxide system according to claim 1 precursor, it is characterised in that
The tap density of the precursor is more than 2.0g/cc.
8. before a kind of anode active material, the composite transition metal oxide system any one of its usage right requirement 1~7
Body and lithium precursor and manufacture.
9. anode active material according to claim 8, it is characterised in that nickel (Ni) content is in whole transition metal
More than 60%.
10. the manufacture method of composite transition metal oxide system according to any one of claims 1 to 7 precursor, it includes will
Composite transition metal hydroxide represented by following chemical formula 2 is under air atmosphere or oxygen atmosphere with 700~1100 DEG C
The step of temperature carries out the heat treatment of 1~12 hour：
[chemical formula 2]
NiaCobM’c(OH)2
In the formula,
M ' is to select free alkali metal, alkaline-earth metal, 13 race's elements, 14 race's elements, 15 race's elements, 16 race's elements, 17 race's elements, mistake
One or more of group of metal and rare earth element composition is crossed,
0.6≤a<1.0,0≤b≤0.4,0≤c≤0.4, a+b+c=1.
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| KR102362778B1 (en) * | 2019-11-29 | 2022-02-11 | 삼성에스디아이 주식회사 | Positive active material precursor, positive active material, method of preparing the same, positive electrode including the same and rechargeable lithium battery including the same |
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| CN101281965A (en) * | 2008-05-29 | 2008-10-08 | 复旦大学 | Positive electrode material of Li-ion battery and preparing process thereof |
| CN101609893A (en) * | 2008-06-16 | 2009-12-23 | 中信国安盟固利新能源科技有限公司 | Lithium ion secondary battery anode material and preparation method thereof |
| CN101847722A (en) * | 2009-03-26 | 2010-09-29 | 青岛新正锂业有限公司 | High-performance lithium ion battery cathode material and preparation method thereof |
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| CN101609893A (en) * | 2008-06-16 | 2009-12-23 | 中信国安盟固利新能源科技有限公司 | Lithium ion secondary battery anode material and preparation method thereof |
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