CN109314238A - Metal-doped high voltage positive electrode active materials - Google Patents

Metal-doped high voltage positive electrode active materials Download PDF

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CN109314238A
CN109314238A CN201780036217.XA CN201780036217A CN109314238A CN 109314238 A CN109314238 A CN 109314238A CN 201780036217 A CN201780036217 A CN 201780036217A CN 109314238 A CN109314238 A CN 109314238A
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positive electrode
electrode active
active materials
lithium
weight
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CN109314238B (en
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朴星彬
朴英旭
朴知伶
李宝蓝
赵治皓
许赫
郑王谟
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LG Energy Solution Ltd
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LG Chemical Co Ltd
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract

The present invention relates to a kind of high voltage positive electrode active materials and preparation method thereof of metallic element doping, wherein the positive electrode active materials can be the material including following components: the lithium and cobalt oxides with layer structure；With the lithium and cobalt oxides relative to 100 parts by weight, the metallic element (M) being doped to the amount of 0.2 parts by weight to 1 parts by weight in the lithium and cobalt oxides, wherein, crystal structure is able to maintain in the range of the anodic potentials in full charge are greater than 4.5V (being based on Li current potential).

Description

Metal-doped high voltage positive electrode active materials
Technical field
Cross reference to related applications
The application based on and require respectively at the Korean Patent Shen that on December 21st, 2016 and on December 18th, 2017 submit Priority that please be No. 10-2016-0175204 and No. 10-2017-0174513, by quoting the disclosure of which completely simultaneously Enter herein.
The present invention relates to a kind of metal-doped high voltage positive electrode active materials and preparation method thereof.
Background technique
With technology development and the increase to mobile device demand, the demand to the secondary cell as the energy increases rapidly Add, and in these secondary cells, the secondary electricity of lithium with high-energy density and operating potential, long-life and low self-discharge rate Pond has been commercialized and has been widely used.
In addition, being carried out to electric vehicle and hybrid electric vehicle with the growing interest to environmental problem Many researchs, the vehicle using fossil fuel of one of the main reason for being substituted for as air pollution is (for example, vapour Oily vehicle, diesel vehicle etc.).Although ni-mh metal secondary batteries have been mainly used as electric vehicle and hybrid electric vehicle Power source, but the application of the lithium secondary battery with high-energy density and discharge voltage is actively had studied, and wherein It is some commercially available.
As the positive electrode of lithium secondary battery, LiCoO has been used2, ternary material (NMC/NCA), LiMnO4、LiFePO4 Deng.LiCoO2Due to excellent physical property (such as high calendering density etc.) and excellent electrochemical properties (such as Gao Xun Ring property) and be frequently used up to now.However, due to LiCoO2With the charge/discharge current down to about 150mAh/g Capacity, and its structure is unstable under the high voltage of 4.3V or more, thus its have the problem of life characteristic reduces rapidly and Cause the problem of catching fire with reacting for electrolyte.
In particular, when in order to develop high-capacity secondary battery and to LiCoO2When applying high voltage, LiCoO2Li using increase Add, a possibility that this can increase unstable surface and structural instability.In order to solve these problems, by using other elements Part cobalt is replaced to replace LiCoO2, or by forming individual coating develop positive electrode.
However, being also difficult to improve LiCoO in the positive electrode with above-mentioned substitution or coating2Structural stability.It is special It is not, under the high voltage greater than 4.5V, it is difficult to keep structural stability.In practice, it may be difficult to by LiCoO2Applied to high capacity Secondary cell.
In addition, in LiCoO2Cated positive electrode is formed on surface, coating hampers during charge/discharge cycle Hinder the movement of Li ion or reduces LiCoO2Capacity, the problem of may deteriorate accordingly, there exist the performance of secondary cell.
Therefore, to the lithium and cobalt oxides that can ensure that structural stability and performance do not deteriorate under the high voltage greater than 4.5V The demand of class positive electrode active materials is continuously increased.
Summary of the invention
[technical problem]
Therefore, the present invention, which provides, can ensure structural stability and performance does not deteriorate under a kind of high voltage greater than 4.5V Positive electrode active materials and preparation method thereof.
In addition, the present invention provides a kind of anode comprising the positive electrode active materials and a kind of lithium secondary battery comprising The anode is to show excellent performance and life characteristic under the high voltage greater than 4.5V.
[technical solution]
Therefore, the present invention provides a kind of positive electrode active materials, and it includes the lithium cobalt oxidations of the layer structure indicated by following formula 1 Object；With
Metallic element (M), relative to the lithium and cobalt oxides of 100 parts by weight, the metallic element (M) is with 0.2 weight The amount of part to 1 parts by weight is doped in the lithium and cobalt oxides, wherein the positive electrode active materials being higher than in full charge Crystal structure is kept under the anodic potentials (being based on Li current potential) of 4.5V:
[formula 1]
Li1+xCo1-xO2
Wherein, x meets 0≤x≤0.2；With
M is the group formed selected from the metal for being+2 or+3 by Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb and oxidation number More than one.
In addition, the present invention provides a kind of lithium secondary battery comprising: the anode containing the positive electrode active materials；Cathode； And electrolyte.
In addition, the present invention provides a kind of preparation method of positive electrode active materials, the method includes by cobaltatess, lithium The precursor process dry-mixed with doping precursor；With 900 DEG C or more at a temperature of be sintered the mixture process.
Hereinafter, the positive electrode active materials and preparation method thereof that the specific embodiment of the invention will be described.
According to embodiment of the present invention, a kind of positive electrode active materials are provided, it includes the layers indicated by following formula 1 The lithium and cobalt oxides of shape structure；With
Metallic element (M), relative to the lithium and cobalt oxides of 100 parts by weight, the metallic element (M) is with 0.2 weight The amount of part to 1 parts by weight is doped in the lithium and cobalt oxides, wherein the positive electrode active materials being higher than in full charge Crystal structure is kept under the anodic potentials (being based on Li current potential) of 4.5V:
[formula 1]
Li1+xCo1-xO2
Wherein, x meets 0≤x≤0.2；With
M is the group formed selected from the metal for being+2 or+3 by Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb and oxidation number More than one.
The present inventor has been carried out lasting further investigation, and as described in more detail below, discovery, which is worked as, has layer When the lithium and cobalt oxides of the formula 1 of shape structure are doped with more than predetermined amount more than one metallic element, in the height for being greater than 4.5V The structural stability of crystal structure can be improved under voltage, to keep stable crystal structure, thus realize high voltage characteristics, by This completes the present invention.
As used herein, by metallic element " doping " mean into lithium and cobalt oxides the metallic element not with lithium cobalt oxidation Object and its element form chemical bond, but in the lattice structure of at least partly metallic element M incorporation lithium and cobalt oxides, to have Physics/crystallography connection.In this respect, at least partly metallic element M mixed in the lattice structure of lithium and cobalt oxides can example Such as mix in the void space of the lattice structure of lithium and cobalt oxides with the connection of physics/crystallography without with lithium and cobalt oxides shape At chemical bond.In this way, since metallic element M has physics/crystallography connection without forming chemical bond, metal with lithium and cobalt oxides Element M can be mainly distributed in the region on lithium and cobalt oxides surface.
Therefore, " doping " can be clearly distinguished from the state of metallic element M and lithium and cobalt oxides formation chemical bond, example Such as, the part cobalt being different from lithium and cobalt oxides is replaced by metallic element M, then metallic element M is chemically bonded to oxide Combined state.Under combined state, metallic element M can be evenly distributed in lithium cobalt by the formation of chemical bond or complex The whole region of oxide.
In this way, the positive electrode active materials of an embodiment have based on the formula 1 doped with more than one metallic elements Therefore dopant more than predetermined amount is mixed and is placed in the lattice of lithium and cobalt oxides, to mention by the structure of lithium and cobalt oxides The stability of high crystal structure and particle surface.
Particularly, the positive electrode active materials of an embodiment may include the dopant of predetermined amount or more, such as 0.2 weight Part or more or 0.2 parts by weight to 1.0 parts by weight or 0.3 parts by weight to 0.9 parts by weight are measured, thus even if in 4.3V or more or big The crystal structure of lithium and cobalt oxides can also be stablized under the high voltage of 4.5V.It is thus identified that the positive electrode active materials can be excellent Select the active material for showing excellent capacity and life characteristic under high voltages.
On the contrary, until 4.45V, positive electrode active materials are in capacity and knot when the doping of dopant is less than 0.2 parts by weight It is all excellent in terms of structure stability.However, occurring to collapse there are structure or service life rapid degradation being asked under the voltage higher than 4.5V Topic.In addition, when the doping of dopant be greater than 1.0 parts by weight it is excessively a large amount of when, or when metallic element by chemical bond with When lithium and cobalt oxides form complex (for example, complex that part cobalt is changed into metallic element M) rather than adulterate, or work as shape When at coating comprising metallic element, the structural stability of active material be may deteriorate under high voltages, the element of replacement or painting Layer may interfere the movement of Li ion during charge/discharge cycle, or the capacity characteristic of the active material based on formula 1 may Due to being deteriorated with respect to reduction for cobalt content.
Meanwhile it as shown in fig. 6, can be for example, by analyzing above-mentioned work by TOF-SIMS (time of flight secondary ion massspectrometry) Property material result at least partly metallic element M is mixed in the lattice of lithium and cobalt oxides to be identified through doping.It confirmed Metallic element M is mainly distributed in the region on lithium and cobalt oxides surface, shows that at least partly metallic element M has been doped to lithium In cobalt/cobalt oxide, and complex is not formed by chemical bond and lithium and cobalt oxides.
In addition, in a specific embodiment, positive electrode active materials can be greater than 4.5V and 4.8V charging below Crystal structure is kept in range, specifically, positive electrode active materials can be protected being greater than in 4.5V and 4.6V chargeable range below The stability of crystal structure is held, more specifically, positive electrode active materials can be greater than in 4.5V and 4.55V chargeable range below Ensure the stability of crystal structure.
Above-mentioned dopant metal element M can selected from be by Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb and oxidation number+ The metallic element group of 2 or+3 metal composition, and be not particularly limited.However, it is contemplated that reducing secondary anti-with the surface of electrolyte It answers or phase stability under high voltages, metallic element M can be Al or Mg.In some cases, whole Al and Mg are ok As dopant.
Meanwhile in another specific embodiment, when the positive electrode active materials of an embodiment charge under high voltages Crystal structural stability can be kept, and this stability can confirm by XRD analysis.For example, in positive-active material In 2 θ scales of the XRD analysis result of material, the peak intensity in (003) face under 4.55V can be the peak in (003) face under 4.50V 30% or more of intensity.More specifically, the peak intensity in (003) face under 4.55V can be 4.50V in 2 θ scales of XRD diagram Under (003) face peak intensity 40% or more or 40% to 90%.
In other words, the peak intensity of measurement (003) face (crystal face for indicating lithium ion entrance in lithium and cobalt oxides) can be passed through Degree is to confirm whether lithium and cobalt oxides keep crystal structure.When charging to 4.55V, previous lithium and cobalt oxides show crystal The collapsing of structure, therefore compared with the peak intensity of 4.5V, measure significant low peak intensity.Thus, it will be seen that working as lithium cobalt oxide When compound does not have metal-doped or a small amount of doping, the collapsing of crystal structure may occur under the voltage greater than 4.5V.
However, since the positive electrode active materials of an embodiment include the dopant of certain content and type, The peak intensity in (003) face under 4.55V can be 30% or more of the peak intensity in (003) face under 4.5V, show in high voltage The improvement of flowering structure stability.
In yet another embodiment, in full charge under the anodic potentials of 4.5V (being based on Li current potential), metallic element (M) doping content (b) can show for the positive electrode active materials of 0.3 parts by weight The low capacity retention ratio of the positive electrode active materials of 0.1 parts by weight.
In this way, even if the doping content of metallic element is relatively high, but in full charge under the current potential of 4.5V, due to height The dopant of content, capacity retention ratio may be decreased.Therefore, in order to realize high capacity conservation rate, the anode of an embodiment The charging voltage of doping metals and at least above 4.5V that active material needs to have high-content.
For example, Mg content is that the positive electrode active materials of 0.3 parts by weight are recycled at 30 when the metallic element of doping is Mg The capacity lower than the positive electrode active materials that Mg doping content is 0.1 parts by weight can be shown after above charge/discharge cycle Conservation rate.
That is, positive electrode active materials exist when lithium cobalt positive electrode active materials are 0.3 parts by weight doped with the content of Mg and Mg Appearance more higher than the positive electrode active materials that Mg content is 0.1 parts by weight is shown after the charge/discharge cycle recycled less than 30 Conservation rate is measured, but after charge/discharge cycle is greater than 30 circulations, shows the anode than Mg content for 0.1 parts by weight The lower capacity retention ratio of active material.
Therefore, in the case where charging voltage is 4.5V, even if using a large amount of dopant, but with charge/discharge cycles Increase, capacity retention ratio may be decreased and life characteristic may deteriorate.
On the contrary, under the anodic potentials (being based on Li current potential) of the 4.55V in full charge, the doping content of metallic element (M) (b) be 0.3 parts by weight positive electrode active materials can show be than the doping content of metallic element (M) 0.1 parts by weight just The high capacity retention ratio of pole active material.
In this way, one embodiment is just in order to realize the high capacity conservation rate under the high charge voltage greater than 4.5V Pole active material is needed comprising dopant more than predetermined amount.From charging voltage be 4.5V the case where it is different, although doping metals It is Mg, but the positive electrode active materials that doping content is 0.3 parts by weight can show after 30 or more charge/discharge cycles The capacity retention ratio higher than the positive electrode active materials that doping content is 0.1 parts by weight out.
In addition, doping metals content is positive electrode active materials and the doping of 0.3 parts by weight in the case where charging voltage is 4.55V Capacity retention ratio difference of the tenor between the positive electrode active materials of 0.1 parts by weight is with charge/discharge cycles Increase and gradually increases.
For example, 4.55V when using the positive electrode active materials that doping metals content is 0.3 parts by weight, in full charge Anodic potentials (be based on Li current potential) under, the capacity retention ratio after the charge/discharge cycle that 50 recycle can be initially 85% or more of capacity is with the doping metals content for typically exhibiting the capacity retention ratio less than 75% after same loop The positive electrode active materials of 0.1 parts by weight are compared, and show high life characteristic.
In a specific embodiment, the positive electrode active materials of said one embodiment can be further contained in lithium The coating formed on cobalt oxide particles, and the coating may include selected from by Al2O3、MgO、ZrO、Li2ZrO3And TiO2Group At group more than one metal oxides.The formation of the coating can be further improved the stable structure of lithium and cobalt oxides particle Property.
In general, being released when using lithium and cobalt oxides as positive electrode active materials under high voltages from lithium and cobalt oxides particle A large amount of lithium ion is released, and the Li ion concentration on surface is lower, to be easy release Co.As the release of Co increases, Reversible capacity reduces, and Co increases a possibility that being precipitated in negative terminal surface, this can increase negative electricity resistance.Therefore, when When being further formed coating of metal oxides on lithium and cobalt oxides particle, the metallic element that includes in coating can prior to cobalt with HF reaction, to protect positive electrode active materials particle.As a result, the cycle characteristics that can be effectively prevented secondary cell under high voltage is bad Change.
The content of the content of lithium and cobalt oxides based on formula 1, the metallic element for including in coating can control in 300ppmw To 1,200ppmw.When the content for the metallic element for including in coating is less than 300ppmw, it is difficult to ensure positive electrode active materials Structural stability.When the content is greater than 1,200ppmw, the capacity and output characteristics of battery are undesirably deteriorated.
Meanwhile according to the present invention another embodiment there is provided a kind of anode for preparing said one embodiment is living The method of property material.The preparation method may include by cobaltatess, lithium precursor and adulterating the dry-mixed process of precursor；And 900 DEG C or more at a temperature of be sintered the process of the mixture.
The present inventor's the experimental results showed that, doped with embodiment of at least partly metallic element M Active material can be by the way that by precursor, dry-mixed merging is sintered the mixture at high temperature and prepares each other.It is different from this method, when When using other wet processes such as co-precipitation, active material is by the chemical bond between metallic element M and formula 1 with complex form It obtains, it is therefore more likely that the positive electrode active materials of an embodiment can not be prepared.
In the preparation method of above-mentioned another embodiment, sintering temperature can be such as 900 DEG C to 1, and 200 DEG C, specifically Ground, 1,000 DEG C to 1,100 DEG C, and sintering time can be 4 hours to 20 hours, specifically, 5 hours to 15 hours.
When sintering temperature is lower than 900 DEG C, possibly it can not be properly formed the structure of lithium and cobalt oxides, and work as sintering temperature When higher than 1200 DEG C, lithium and cobalt oxides excess agglomeration deteriorates so as to cause capacity or life characteristic, this is undesirable.In addition, When sintering time is shorter than 4 hours, it may occur that adulterate insufficient problem, when sintering time be 12 it is small when more than when, lithium The physics and chemical property of cobalt/cobalt oxide may change, and so as to cause performance deterioration, this is undesirable.
After sintering process, this method may further include the table in the lithium and cobalt oxides doped with metallic element M The process of coating is formed on face.As described above, the coating may include selected from by Al2O3、MgO、ZrO、Li2ZrO3And TiO2Composition Group more than one metal oxides.
In one embodiment, in order to form coating, metallic element in the coating can will be included comprising plan Salt is mixed with doped lithium and cobalt oxides, then can be sintered the mixture.That is, forming cated positive-active material thereon Material can be by will include that the salt of metallic element is applied on the particle surface of doped lithium and cobalt oxides and then is sintered To prepare.
Meanwhile the type of the cobalt/cobalt oxide used in the preparation method of above-mentioned another embodiment is not particularly limited, But cobaltatess can be for example selected from by Co3O4、CoCO3、Co(NO3)2With Co (OH)2The group of composition more than one, especially Co3O4Or Co (OH)2。
Lithium precursor can be selected from by Li2CO3、LiOH、LiNO3、CH3COOLi and Li2(COO)2The group of composition it is a kind of with On, especially LiOH or Li2CO3。
Doping precursor can be selected from the following group more than one: selected from by Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, More than one metals for the group that the metal that Nb and oxidation number are+2 or+3 forms, metal oxide and its metal salt；Especially Al and/or Mg.
Meanwhile another embodiment according to the present invention, provide a kind of anode comprising said one embodiment The anode of secondary cell of active material.
Anode can for example, by will include the positive electrode active materials being made of positive electrode active materials particle, conductive material and The anode mixture of adhesive is applied on positive electrode collector to manufacture, and as needed, filler can be further added to just In the mixture of pole.
Positive electrode collector is usually fabricated to the thickness with 3 μm to 500 μm.Positive electrode collector is not particularly limited, only Want its chemical change with high conductivity without causing respective battery.Positive electrode collector can be for example selected from stainless Any one of steel, aluminium, nickel, titanium and surface carbon, nickel, titanium or the processed aluminium of silver or stainless steel.Particularly, it can be used Aluminium.Collector can be by forming the fine coarse adherency to increase positive electrode active materials on the surface.For example, collector can To be various forms, such as film, piece, foil, net, porous material, foamed material, nonwoven cloth material etc..
Positive electrode active materials can be made of positive electrode active materials particle and following components: lamellar structure compound (such as Lithium nickel oxide (LiNiO2)), or replace the compound for having more than one metals；Lithium manganese oxide, such as formula Li1+xMn2-xO4 (wherein, x is 0 to 0.33), LiMnO3、LiMn2O3、LiMnO2Deng；Lithium Cu oxide (Li2CuO2)；Barium oxide, such as LiV3O8、LiV3O4、V2O5、Cu2V2O7Deng；By formula LiNi1-xMxO2(wherein, M is Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x 0.01 to 0.3) indicate Ni bit-type lithium nickel oxide；By formula LiMn2-xMxO2(wherein, M is Co, Ni, Fe, Cr, Zn or Ta, And x is 0.01 to 1) or Li2Mn3MO8The complex Li-Mn-oxide that (wherein, M is Fe, Co, Ni, Cu or Zn) indicates； LiMn2O4, wherein some Li in formula are replaced by alkaline-earth metal；Disulphide；Fe2(MoO4)3Deng, but not limited to this.
Based on the total weight of mixture containing a positive electrode active material, the additive amount of conductive material be usually 0.1 weight % extremely 30 weight %.Conductive material is not particularly limited, as long as its conductive chemical change without causing respective battery. The example of conductive material may include: graphite, such as natural or artificial graphite；Carbon black, such as carbon black, acetylene black, Ketjen black, slot Black, furnace black, lampblack, thermal crack black etc.；Conductive fiber, such as carbon fiber, metallic fiber etc.；Metal powder, such as fluorocarbons, Aluminium, nickel powder etc.；Conductive whiskers, such as zinc oxide, potassium titanate etc.；Conductive metal oxide, such as titanium oxide etc.；Polyphenylene spreads out Biology etc..
The bonding and collector is glued that the adhesive for including in anode contributes between active material and conductive agent The component of conjunction, and the total weight based on mixture containing a positive electrode active material, the additive amount of adhesive typically 0.1 weight Measure % to 30 weight %.The example of adhesive may include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), form sediment Powder, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, ethylene-propylene-two Alkene terpolymer (EPDM), sulfonated epdm, SBR styrene butadiene rubbers, fluorubber, various copolymers etc..
Include above-mentioned anode, cathode and lithium secondary battery of electrolyte embodiment there is provided a kind of according to another.Lithium two The type of primary cell is not particularly limited, but lithium secondary battery may include for example with high-energy density, discharge voltage, output The lithium ion battery or lithium ion polymer battery of the advantages that stability.
In general, lithium secondary battery is made of anode, cathode, diaphragm and non-aqueous electrolyte containing lithium salts.
Hereinafter, the other components that lithium secondary battery will be described.
Cathode can be manufactured by the way that negative electrode active material to be applied on negative electrode collector and then be dried.According to need It wants, optionally may further include said components.
The thickness with 3 μm to 500 μm usually is made in negative electrode collector.Negative electrode collector is not particularly limited, as long as Its conductive chemical change without causing respective battery.It is, for example, possible to use copper, stainless steel, aluminium, nickel, titanium, forge Burn the processed copper such as carbon or surface carbon, nickel, titanium, silver or stainless steel and aluminium cadmium alloy etc..It is identical as positive electrode collector, it bears Electrode current collector can have the fine coarse adherency to enhance negative electrode active material on the surface thereof, and can be with various shapes Formula uses, such as film, piece, foil, net, porous material, foamed material, nonwoven cloth material etc..
Negative electrode active material may include for example: carbon, such as ungraphitised carbon, graphitized carbon etc.；Composite oxide of metal, Such as LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe’yOz(Me:Mn, Fe, Pb, Ge；Me ': Al, B, P, Si, period of element Table I, II or group-III element, halogen；0<x≤1；1≤y≤3；1≤z≤8) etc.；Lithium metal；Lithium alloy；Silicon Class alloy；Tin class alloy；Metal oxide, such as SnO, SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、 GeO、GeO2、Bi2O3、Bi2O4And Bi2O5Deng；Conducting polymer, such as polyacetylene etc.；Li-Co-Ni class material.
Diaphragm uses the insulation film with high ion permeability and mechanical strength between anode and cathode. Diaphragm usually has 0.01 μm to 10 μm of aperture and 5 μm to 300 μm of thickness.As diaphragm, for example, using by olefinic polymerization The piece or non-woven fabrics that object (such as with chemical resistance and hydrophobic polypropylene) or glass fibre or polyethylene are formed.When adopting When using the solid electrolytes such as polymer as electrolyte, solid electrolyte can also function simultaneously as diaphragm and electrolyte.
Non-aqueous electrolyte containing lithium salt is made of non-aqueous electrolyte and lithium salts.Non-aqueous electrolyte may include non-aqueous Property organic solvent, organic solid electrolyte or inorganic solid electrolyte, but not limited to this.
Non-aqueous Organic Solvents can be such as aprotic organic solvent, such as n-methyl-2-pyrrolidone, polypropylene carbonate Ester, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1,2- dimethoxy-ethane, four Hydroxyl Frank (franc), 2- methyltetrahydrofuran, dimethyl sulfoxide, 1,3- dioxolanes, formamide, dimethylformamide, Dioxolanes, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolanes are derivative Object, sulfolane, methyl sulfolane, 1,3- dimethyl -2- imidazolidinone, polypropylene carbonate ester derivant, tetrahydrofuran derivatives, second Ether, methyl propionate, ethyl propionate etc..
Organic solid electrolyte may include that such as polythene derivative, polyethylene oxide derivatives, polypropylene oxide are spread out Biology, poly-stabilized lysine (polyagitation lysine), polyester sulfide, polyvinyl alcohol, gathers inclined two at phosphate ester polymer Vinyl fluoride, polymer containing ionic dissociation groups etc..
Inorganic solid electrolyte may include such as Li class nitride, halide or sulfate, such as Li3N、LiI、 Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH、 Li3PO4-Li2S-SiS2Deng.
Lithium salts is the substance for being soluble in non-aqueous electrolyte, may include such as LiCl, LiBr, LiI, LiClO4、LiBF4、 LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi, chloroborane lithium, lower aliphatic lithium carboxylate, tetraphenylboronic acid lithium, acid imide etc..
In order to improve charge/discharge characteristics and anti-flammability, such as pyridine, phosphorous acid can be added in non-aqueous electrolyte Triethyl, triethanolamine, cyclic ethers, ethylenediamine, glycol dimethyl ether, hexaphosphoric acid triamide, nitrobenzene derivative, sulphur, quinone imines Dyestuff, N- replace oxazolidone, N, N- replace imidazolidine, glycol dialkyl ether, ammonium salt, pyrroles, 2-methyl cellosolve, Alchlor etc..It is alternatively possible to add the halogen-containing solvent such as carbon tetrachloride or trifluoro-ethylene further to provide resistance Combustion property, or carbon dioxide gas can be added further to improve high temperature retention performance, and can further add FEC (carbonic acid fluorinated ethylene ester), PRS (propene sultone) etc..
It is according to the present invention it is another embodiment there is provided a kind of battery packs comprising secondary cell, and include the electricity The equipment of pond group.Above-mentioned battery pack and equipment are known in the art, and therefore, will omit its specific descriptions in the present invention.
The equipment can be such as laptop, net book, tablet computer, mobile phone, MP3, wearable electronic and produce Product, electric tool, electric vehicle (EV), hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV), Electric bicycle, Segway Human Transporter, electric golf cart or power storage system etc., but not limited to this.
[beneficial effect]
As described above, positive electrode active materials of the invention have in the lithium and cobalt oxides of layer structure doped with one kind with Therefore dopant more than predetermined amount is mixed and is placed in the lattice of lithium and cobalt oxides by the structure of upper metallic element, thus The collapsing of crystal structure is prevented under high voltage greater than 4.5V and ensures structural stability.
Different from ternary system, the capacity of lithium and cobalt oxides is only increased by increasing voltage.However, when using the present invention Positive electrode active materials when, can solve the stability problem under high voltage, to realize high capacity and high circulation characteristic.
Detailed description of the invention
It is when charging under 4.5V, comprising doped with 1,000ppm or 3, the lithium of 000ppm Mg that Fig. 1, which is shown in upper limit voltage, The figure of the capacity retention ratio of Coin shape (coin-type) half-cell of cobalt/cobalt oxide；
It is when charging under 4.55V, comprising doped with 1,000ppm or 3, the lithium of 000ppmMg that Fig. 2, which is shown in upper limit voltage, The figure of the capacity retention ratio of the coin-like half cells of cobalt/cobalt oxide；
It is when charging under 4.5V, comprising doped with 1,000ppm or 3, the lithium of 000ppm Al that Fig. 3, which is shown in upper limit voltage, The figure of the capacity retention ratio of the coin-like half cells of cobalt/cobalt oxide；
Fig. 4 is shown in upper limit voltage, comprising doped with 1,000ppm or 3,000ppm Al's The figure of the capacity retention ratio of the coin-like half cells of lithium and cobalt oxides；
Fig. 5 shows TOF-SIMS (time of flight secondary ion massspectrometry) the analysis knot of the positive electrode active materials of embodiment 1 Fruit；With
Fig. 6 is the peak intensity for showing the coin-like half cells of the positive electrode active materials comprising embodiment 1 or comparative example 1 XRD diagram is measured when upper limit voltage is increased to 4.54V from 4.5V with the interval of 0.01V.
Specific embodiment
Embodiments of the present invention are described below with reference to attached drawing.However, providing these embodiments merely to more preferable Ground understands, but the scope of the present invention is not limited thereto.
The preparation of positive electrode active materials
<embodiment 1>
By the Co of MgO, 80.27g of 0.294g3O4With the Li of 36.94g2CO3It is dry-mixed each other, so that being based on positive-active material The total weight of material, the content of Mg are 3,000ppm.Then, mixture is sintered 10 hours in 1050 DEG C of furnace, to prepare Mg The lithium and cobalt oxides of doping.
<embodiment 2>
By the Al of 0.147g2O3, 80.27g Co3O4With the Li of 36.94g2CO3It is dry-mixed each other, so that being based on positive-active The total weight of material, the content of Al are 3,000ppm.Then, mixture is sintered 10 hours in 1050 DEG C of furnace, with preparation The lithium and cobalt oxides of Al doping.
<embodiment 3>
By the Co of MgO, 80.27g of 0.245g3O4With the Li of 36.94g2CO3It is dry-mixed each other, so that being based on positive-active material The total weight of material, the content of Mg are 5,000ppm.Then, mixture is sintered 10 hours in 1050 DEG C of furnace, to prepare Al The lithium and cobalt oxides of doping.
<embodiment 4>
By the Co of MgO, 80.27g of 0.343g3O4With the Li of 36.94g2CO3It is dry-mixed each other, so that being based on positive-active material The total weight of material, the content of Mg are 7,000ppm.Then, mixture is sintered 10 hours in 1050 DEG C of furnace, to prepare Al The lithium and cobalt oxides of doping.
<embodiment 5>
By the Co of MgO, 80.27g of 0.441g3O4With the Li of 36.94g2CO3It is dry-mixed each other, so that being based on positive-active material The total weight of material, the content of Mg are 9,000ppm.Then, mixture is sintered 10 hours in 1050 DEG C of furnace, to prepare Al The lithium and cobalt oxides of doping.
<embodiment 6>
In order to form coating on the lithium and cobalt oxides of the Mg doping prepared in embodiment 1, by the Al of 500ppm2O3With lithium Cobalt oxide particles are dry-mixed to coat lithium and cobalt oxides particle, are then sintered 5 hours in 700 DEG C of furnace, to prepare shape thereon At cated positive electrode active materials.
<comparative example 1>
The lithium and cobalt oxides of Mg doping are prepared in the same manner as example 1, the difference is that, it is based on positive-active The total weight of material, the content of Mg are 1,000ppm.
<comparative example 2>
The lithium and cobalt oxides of Al doping are prepared in the same way as in example 2, the difference is that, it is based on positive-active The total weight of material, the content of Al are 1,000ppm.
<comparative example 3>
The lithium and cobalt oxides of Mg doping are prepared in the same manner as example 1, the difference is that, it is based on positive-active The total weight of material, the content of Mg are 10,000ppm.
The manufacture of secondary cell
Each metal-doped positive electrode active materials, the PVdF adhesive that will be prepared in embodiment 1 to 6 and comparative example 1 to 3 It is sufficiently mixed in NMP with the weight ratio (positive electrode active materials: adhesive: conductive material) of 96:2:2 with natural graphite conductive material It closes, is then applied on the Al foil with a thickness of 20 μm, and is dry at 130 DEG C, to manufacture each anode.As cathode, make With lithium foil, using containing 1MLiPF in the solvent of EC:DMC:DEC=1:2:16Electrolyte manufacture half electricity of each Coin shape Pond.
<the analysis of experimental example 1>capacity retention ratio
Each coin-like half cells manufactured above are charged into upper limit voltage 4.5V or 4.55V at 25 DEG C with 0.5C, Then lower voltage limit 3V is discharged to 1.0C.This process is considered as 1 circulation, and measures the capacity after 50 circulations and keep Rate.As a result the following table 1 and Fig. 1 are shown in in 4.Table 2 shows initial capacity when charging respectively with 4.5V and 4.55V.
[table 1]
[table 2]
Reference table 1, Fig. 1 to 4 and table 2, when adulterating Mg or Al of 3,000ppm as in embodiment 1 or 2, in 4.5V After 50 charge/discharge cycles of lower progress, capacity retention ratio is lower than the appearance of the comparative example 1 or 2 of the Mg or Al doped with 1000ppm Measure conservation rate.Fig. 1 is shown, when using the positive electrode active materials of embodiment 1, until about 30 circulations, capacity retention ratio are all high In the capacity retention ratio of comparative example 1, but after more than 30 times circulations, the capacity retention ratio of embodiment 1 is reduced rapidly.
However, the Examples 1 and 2 with more highly doped content show after carrying out 50 charge/discharge cycles with 4.55V Considerably higher capacity retention ratio out.
Al doping content is that the embodiment 2 of 3,000ppm shows the capacity retention ratio lower than at 4.55V at 4.5V. However, comparing with Al doping content for the comparative example 1 of 1,000ppm, its capacity retention ratio is reduced at 4.5V, and at 4.55V Its capacity retention ratio increases.
Meanwhile Mg doping content is that the comparative example 2 of 10,000ppm shows low capacity retention ratio compared to the examples,.
This is because positive electrode active materials undergo reversible transition during charge/discharge, and with the increasing of charging potential Add, the invertibity of phase transformation reduces, so as to cause the reduction of capacity.However, when in order to prepare the high potential lithium cobalt with high capacity Oxide and in lithium and cobalt oxides adulterate particular range in metal when, irreversible transition can be made to minimize, to prevent The decline of capacity retention ratio.However, when the content of doping metals is too small as in comparative example 1 and 2, it is difficult to obtain above-mentioned effect Fruit, and therefore declined rapidly with capacity retention ratio when 4.55V progress charge/discharge.
Therefore, when lithium and cobalt oxides are doped with Mg or Al within the scope of certain content, the phase transformation under high potential can be made It minimizes, to show high capacity retention ratio.
In addition, starting efficiency reduces under the voltage higher than 4.5V with the increase of doped chemical content, it is therefore contemplated that Balance anode and cathode are easy when manufacturing battery unit.It is also contemplated that the surplus of positive electrode active materials is reduced, this will be helpful to drop The production cost of low battery unit.Therefore, it is contemplated that the material for being suitable for the operation voltage conditions of battery unit can be designed, it can be with Performance needed for realizing battery unit, and production cost can be greatly reduced.
Meanwhile at 4.55V, with the increase of Mg doping, the service life slightly improves, it is speculated that due to stable structure Change.However, with the increase of Mg doping, starting efficiency reduces at 4.55V.It is expected that the doping as Mg increases to 10, When 000ppm or more, it can further promote the resistance increase of positive electrode active materials rather than structural stability, so as to bad Change capacity, and may be decreased lifetime stability.
Meanwhile compared with the embodiment 1 for not having coating, after carrying out 50 charge/discharge cycles with 4.55V, embodiment 6 The cated doped lithium and cobalt oxides of tool show high capacity retention ratio.
Thus, it will be seen that the positive electrode active materials of embodiment show the improved service life under the current potential higher than 4.5V Characteristic.
<experimental example 2>TOF-SIMS (time of flight secondary ion massspectrometry) analysis
Fig. 5, which is shown, analyzes activity material obtained in embodiment 2 by TOF-SIMS (time of flight secondary ion massspectrometry) The result of material.
With reference to Fig. 5, it is thus identified that the metal element A l of doping is distributed on lithium and cobalt oxides, in particular, the metal member of doping Plain Al is mainly distributed in the region on lithium and cobalt oxides surface.These analysis the result shows that, metal element A l is doped to To form physics/crystallography connection in lithium and cobalt oxides, and complex is not formed by chemical bond and lithium and cobalt oxides.
<experimental example 3>XRD analysis
In order to check embodiment 1 and comparative example 1 lithium and cobalt oxides changes in crystal structure, manufactured the coin comprising it Type half-cell, and peak intensity is measured while upper limit voltage is increased to 4.55V from 4.5V with the interval of 0.01V.Such as The XRD diagram (2 θ-scale) of this measurement is shown in Figure 6.
With reference to Fig. 6, the positive electrode active materials of embodiment 1 are shown in the range of 4.40V to 4.55V is in 23 to 24 degree (003) peak in face, and appearance is shown in the range of 24 to 25 degree at 4.55V.When the charging potential of positive electrode active materials When for 4.54V or more, crystal structure carries out phase transformation to another phase, and when charging potential is 4.55V, spends ranges 24 to 25 The new peak of crystal structure after inside observing instruction phase transformation.However, peak of the continuous observation to (003) face to a certain extent, table Bright phase transformation reversibly occurs.Therefore, even if during charge/discharge, capacity retention ratio can also be kept to a certain extent.
Specifically, Fig. 6 shows the peak that phase transformation is front/rear under each voltage.The peak intensity in (003) face under 4.55V It is 30% or more of the peak intensity in (003) face under 4.50V.Metal-doped lithium and cobalt oxides minimize phase transformation, with performance High capacity retention ratio out, to show the life characteristic significantly improved.
However, the positive electrode active materials of comparative example 1 show the peak intensity in significant low (003) face, instruction at 4.55V The peak of crystal structure of the peak height of crystal structure after phase transformation in instruction before phase change, this shows that the invertibity of phase transformation significantly reduces. Thus, it will be seen that life characteristic may be deteriorated substantially when the content of doping metals is low.
For those skilled in the art in the invention it is readily apparent that the case where not departing from the scope of the present invention Under, it can be carry out various modifications and is changed.

Claims (13)

1. a kind of positive electrode active materials, it includes the lithium and cobalt oxides of the layer structure indicated by following formula 1, and
Metallic element (M), relative to the lithium and cobalt oxides of 100 parts by weight, the metallic element (M) is with 0.2 parts by weight to 1 The amount of parts by weight is doped in the lithium and cobalt oxides, wherein the positive electrode active materials are big based on Li current potential in full charge Crystal structure is kept under the anodic potentials of 4.5V:
[formula 1]
Li1+xCo1-xO2
Wherein, x meets 0≤x≤0.2；With
M is the one of the group formed selected from the metal for being+2 or+3 by Al, Ti, Mg, Mn, Zr, Ba, Ca, Ta, Mo, Nb and oxidation number Kind is a variety of.
2. positive electrode active materials according to claim 1, wherein the positive electrode active materials be greater than 4.5V and 4.8V with Under chargeable range in keep crystal structure.
3. positive electrode active materials according to claim 1, wherein M is Al or Mg.
4. positive electrode active materials according to claim 1, wherein the 2 of the XRD analysis result of the positive electrode active materials In θ scale, the peak intensity in (003) face under 4.55V is 30% or more of the peak intensity in (003) face under 4.50V.
5. positive electrode active materials according to claim 1, wherein the 2 of the XRD analysis result of the positive electrode active materials In θ scale, the peak intensity in (003) face under 4.55V is 40% or more of the peak intensity in (003) face under 4.50V.
6. positive electrode active materials according to claim 1, wherein the anode electricity for being 4.5V based on Li current potential in full charge Under position, the doping content of metallic element (M) is that the positive electrode active materials of 0.3 parts by weight show the doping than metallic element (M) Content is the low capacity retention ratio of the positive electrode active materials of 0.1 parts by weight.
7. positive electrode active materials according to claim 6, wherein when the metallic element (M) of doping is Mg, 30 with On charge/discharge cycle after, Mg content is that the positive electrode active materials of 0.3 parts by weight show to be 0.1 weight than Mg doping content Measure the low capacity retention ratio of the positive electrode active materials of part.
8. positive electrode active materials according to claim 1, wherein the anode for being 4.55V based on Li current potential in full charge Under current potential, the doping content of metallic element (M) is that the positive electrode active materials of 0.3 parts by weight show mixing than metallic element (M) Miscellaneous content is the high capacity retention ratio of the positive electrode active materials of 0.1 parts by weight.
9. positive electrode active materials according to claim 1, wherein the anode for being 4.55V based on Li current potential in full charge Under current potential, after 50 charge/discharge cycles, capacity retention ratio is 85% or more of initial capacity.
10. positive electrode active materials according to claim 1 also include the painting formed on the lithium and cobalt oxides particle Layer, wherein the coating includes selected from by Al2O3、MgO、ZrO、Li2ZrO3And TiO2One or more metal oxygens of the group of composition Compound.
11. a kind of lithium secondary battery comprising: just containing positive electrode active materials described in any one of claims 1 to 10 Pole；Cathode；And electrolyte.
12. a method of prepare positive electrode active materials described in claim 1, which comprises
By cobaltatess, lithium precursor and adulterate the dry-mixed process of precursor；With
900 DEG C or more at a temperature of be sintered the mixture process.
13. further including according to the method for claim 12, after the sintering process in the lithium and cobalt oxides The process of coating of metal oxides is formed on grain.
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