CN105702949A - Positive active substance, positive electrode employing same and lithium ion secondary battery - Google Patents
Positive active substance, positive electrode employing same and lithium ion secondary battery Download PDFInfo
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- CN105702949A CN105702949A CN201410713437.XA CN201410713437A CN105702949A CN 105702949 A CN105702949 A CN 105702949A CN 201410713437 A CN201410713437 A CN 201410713437A CN 105702949 A CN105702949 A CN 105702949A
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Abstract
The invention provides a positive active substance capable of preventing the reduction of cycle capacity, an electrode made of the positive active substance and a lithium ion secondary battery. The positive active substance comprises a substance expressed with a general formula of LiMO2 and a solid solution of a lithium-manganese oxide expressed with Li2MnO3 and is provided with a cladding layer, wherein the M in the formula is selected from more than one metal element of Co, Ni and Mn, and the cladding layer wraps at least one part of the positive active substance and contains at least one of rock salt-type LiFeO2, LiFe5O8 and Li5FeO4.
Description
Technical field
The present invention relates to positive active material, use positive pole and the lithium rechargeable battery of this material。
Background technology
In recent years, for solving environment and energy problem, people wait in expectation the universal of various electric motor car。As the vehicle power of critical electromotor power supply in these electric motor cars are practical etc., inquire into the exploitation of lithium rechargeable battery specially。But, in order to make lithium rechargeable battery be widely used as vehicle power, it is necessary to make battery high-performance and cheap。In addition, it is necessary to make electric motor car once charge the distance walked close to petrol engine vehicles, thus needing the battery of higher energy。
Energy density in order to improve battery makes high discharge capacity, it is necessary to improve electricity stored in positive pole and negative pole unit mass。As the positive electrode (positive active material) likely meeting above-mentioned requirements, inquire into the crystal structure with R-3m space group, and on transition metal site, contained the so-called system solid solution material of lithium。But, although system solid solution material finds to have higher capacity in the discharge and recharge of more than 4.6V, it is likely that the oxidation Decomposition of organic bath that the destruction of the crystal structure of positive active material and the raising of charging voltage cause occurs。Capacity when its result is likely to result in circulation reduces。
In order to improve its cycle characteristics, patent documentation 1 proposes with the method for the oxide clad anode active substances such as manganese, nickel, cobalt, zinc。
Patent document 2 also discloses that and uses Al2O3、TiO2、ZrO2、B2O3、SiO2、AlPO4Method Deng oxide clad anode active substance。
Prior art literature
Patent documentation
Patent documentation 1: Chinese patent application discloses 102646830
Patent documentation 2: Japanese Unexamined Patent Publication JP2007-005267A (Patent 2005-187435)
Summary of the invention
Invention is wanted to solve the technical problem that
But, the oxide disclosed in patent documentation 1 yet suffers from the problem that during circulation when high voltage discharge and recharge, capacity reduces。Oxide disclosed in patent documentation 2 does not still fully suppress yet capacity when circulating under high voltage discharge and recharge reduce。
The present invention completes in view of above-mentioned practical situation, it is therefore intended that provide positive active material, the electrode using this material to make and lithium rechargeable battery that capacity when circulating under high voltage discharge and recharge can be suppressed to reduce。
Solve the means of technical problem
In order to achieve the above object, positive active material involved in the present invention has the feature that containing formula LiMO2Lithium composite xoide represented by (M in formula is at least one above metallic element in Co, Ni and Mn) or containing above-mentioned LiMO2With Li2MnO3On the positive active material matrix material of the solid solution of represented lithium manganese oxide, there is at least one of clad being coated with above-mentioned positive active material matrix material, and above-mentioned clad contains selected from rock salt LiFeO2、LiFe5O8、Li5FeO4Middle at least one。
Capacity when circulating under high-voltage charge can be suppressed to reduce by the positive active material that the present invention relates to。This thinks by having above-mentioned clad, the reduction of the capacity that the impact on the crystal structure near positive pole active material surface of generation causes during discharge and recharge can be suppressed, or suppress the oxidation Decomposition of the organic bath caused by the rising of charging voltage, thus suppressing the increase of impedance。Results presumption suppresses capacity when circulating in discharge and recharge to reduce。
Additionally, it is preferred that be coated with above-mentioned clad relative to positive active material matrix material with the amount of 1～15wt%。
This makes it possible to further suppress high voltage discharge and recharge time circulation time inducing capacity fading。
It addition, above-mentioned positive active material matrix material is preferably the second particle that primary particle is aggregated into。
As it has been described above, the present invention can provide positive active material, the electrode using this positive active material and lithium rechargeable battery that capacity when circulating under high voltage discharge and recharge compared with prior art can be suppressed to reduce。
Accompanying drawing explanation
Fig. 1 is the schematic section of the lithium rechargeable battery of the positive active material possessing present embodiment。
Symbol description:
10 ... positive pole, 20 ... negative pole, 12 ... positive electrode collector, 14 ... positive electrode active material layer, 18 ... spacer, 22 ... negative electrode collector, 24 ... negative electrode active material layer, 30 ... laminated body, 50 ... casing, 60,62 ... wire, 100 ... lithium rechargeable battery
Detailed description of the invention
(positive active material)
Hereinafter, as an embodiment of the invention, positive active material, electrode and lithium rechargeable battery are illustrated。But the present invention is not limited to following embodiment。
The positive active material of present embodiment is characterised by, is being LiMO containing formula2(M in formula is at least one above metallic element in Co, Ni and Mn) and Li2MnO3On the positive active material matrix material of the solid solution of represented lithium manganese oxide, having the clad of at least one part being coated with above-mentioned positive active material matrix material, above-mentioned coating layer material at least contains the LiFeO selected from rock salt2、LiFe5O8、Li5FeO4Compound。
Above-mentioned LiFeO2It is preferred for rock-salt type structure, LiFe5O8、Li5FeO4It can be arbitrary crystal structure。These clads are relative to electrolyte stable existence。Namely, think by having these clads, the reduction of the capacity that the destruction of the crystal structure of the positive active material near surface produced when can suppress discharge and recharge causes or the oxidation Decomposition of organic bath caused due to the rising of charging voltage, thus suppressing the increase of impedance。Results presumption suppresses the capacity during circulation in discharge and recharge to reduce。
(positive active material matrix material)
As mentioned above, the positive active material matrix material of present embodiment can enumerate above-mentioned LiMO2(M in formula is at least one above metallic element in Co, Ni and Mn) and Li2MnO3The solid solution of represented lithium manganese oxide, specifically can enumerate the positive active material matrix material represented by composition formula (1)。
LitNipCoqMnr(M3)sO2(1)
[(M3 is chosen from least one in Al, Si, Zr, Ti, Fe, Mg, Nb, Ba and V, wherein 2.0≤(p+q+r+s+t)≤2.2,1.0 < t≤1.3,0 < p≤0.3,0≤q≤0.3,0.3≤r≤0.7,0≤s≤0.1]。
(clad)
The cladding material constituting clad is different from the material of positive active material matrix material, the oxide of Li and Fe。Such as can enumerate LiFeO2、LiFe5O8、Li5FeO4Deng the oxide represented。
Clad can be the layer formed by particulate material。
LiFeO2、LiFe5O8、Li5FeO4In a part can be separated into γ-Fe2O3(bloodstone), it is also possible to partly contain the γ-Fe of surplus2O3。
It addition, LiFeO2、LiFe5O8、Li5FeO4In a part can be separated into Fe3O4(magnetic iron ore), it is also possible to partly contain the Fe of surplus3O4。
A part for Fe element in clad can by more than one the element substitution in Ti, Ni, Co, Mn, Fe, Zr, Cu, Zn and Yb。
As long as it addition, clad produce the degree of the effect of the present invention all without particular limitation of, simply by the presence of and be attached to the surface of positive active material matrix material。It addition, substrate material particle and clad can also partial reactions。Wherein, it is preferable that clad covers more than the 80% of positive active material substrate material surface。
Thus, it is preferable that the clad (B) ratio (δ) relative to positive active material matrix material (A) is 1wt%≤δ≤15wt%。The more preferably amount of 1wt%≤δ≤10wt%。It is hereby achieved that the cycle characteristics that high power capacity is become reconciled。
δ=(B/A) × 100
If ratio (δ) is less than 1wt%, it is possible to occur that cycle performance worsens；If greater than 15wt%, capacity may diminish。
The ratio of clad, for instance can try to achieve in the following manner。
The diffraction pattern first passing through (TransmissionElectronMicroscopy:TEM) of transmission electron microscope tries to achieve the crystal space group of clad, is determined the composition of clad by electron energy loss spectroscopy (EELS) (ElectronEnergy-LossSpectroscopy:EELS)。
The one-tenth of cathode active material is tried to achieve by inductively coupled plasma quality analysis (ICP-MS)。The amount of clad is calculated then in conjunction with known matrix material composition。When the composition of positive active material matrix material is unknown, EELS can be passed through and be measured equally。Ratio is calculated from the composition of the clad obtained and amount。
Additionally, the thickness of clad is preferably more than 10nm and less than 1 μm。Then may be deteriorated by cycle performance if less than 10nm；If greater than 1 μm then capacity may diminish。
The mean diameter of the primary particle of positive active material matrix material is preferably more than 0.05 μm and less than 10 μm。The lithium rechargeable battery using such positive active material can obtain high power capacity。When using the mean diameter active substance less than 0.05 μm of primary particle, there is the reluctant tendency of powder body；When using more than the active substance of 10 μm, there is the tendency that capacity diminishes。It is preferred that average primary particle diameter is more than 0.07 μm and less than 3 μm。
It addition, the average aggregate particle size of positive active material matrix material is preferably more than 3 μm and less than 50 μm。When average aggregate particle size is less than 3 μm, the tendency that the density of electrode can diminish；More than 50 μm, there is the tendency being difficult to make smooth electrode slice, also have the tendency causing internal short-circuit of battery。
(manufacture method of positive active material)
Although the manufacture method of positive active material without particular limitation of, but at least possess raw material modulating process and firing process。According to the lithium source and the source metal that meet the mode of mol ratio shown in composition formula (1) and coordinate regulation, by being pulverized and mixed, thermally decompose mixing, precipitation, or the method such as hydrolysis manufactures。
The method of cladding cladding material on positive active material matrix material is not particularly limited, but at least there is raw material modulating process。In raw material modulating process, so-called wet process can be adopted。It is, for example possible to use the technique being undertaken mixing, stirring by the material solution that the active substance shown in composition formula (1) is constituted with cladding material。As wet method, it is possible to use coprecipitation, sol-gal process, it is possible to be attached to second particle surface。Additionally can also implement the drying process dried before firing process。
Additionally raw material modulating process can use solid phase method, sol-gal process or coprecipitation etc. to make cladding material in advance, then is coated on active substance by this cladding material with mechanochemical reactions such as ball millings。
Cladding material cladding on positive active material matrix material, without particular limitation of being to the cladding of primary particle or the cladding to second particle, but is coated with positive effect to second particle。On the second particle that surface area is little, just can expect covered effect on a small quantity。
The compound in the cladding source metal of material or lithium source without particular limitation of, it is possible to according to known materials such as process choice oxide, salt。
It addition, in order to be able to obtain the active material powder of expectation particle diameter, it is possible to use pulverizer and grader。Such as mortar, ball mill, ball mill, sand mill, vibrator, planetary ball mill, aeropulverizer, counter-jet mill, rotary pneumatic flow pattern aeropulverizer or sieve etc.。When pulverizing, it is possible to use the case of wet attrition of the organic solvent of coexist water or ethane etc.。As stage division, without particular limitation of, it is possible to select according to wet type or dry type and needs and sieve or air classifier etc.。
In active substance, in order to obtain the powder with the active substance of desirable aggregate particle size, it is possible to use spray dryer, it is possible to use other comminutor。
Further, in the present embodiment, by the positive active material obtained by above-mentioned mixed method and cladding material, can burn till in argon atmospher, air atmosphere, oxygen atmosphere, nitrogen atmosphere or their mixed atmosphere。
<lithium rechargeable battery>
With reference to Fig. 1, simple declaration uses positive pole and the lithium rechargeable battery of above-mentioned positive active material making。
Lithium rechargeable battery 100 mainly possesses laminated body 30, receives the casing 50 of laminated body 30 and the couple of conductor 60,62 being connected in laminated body 30 with sealing state。
In laminated body 30, positive pole 10 and negative pole 20 clip spacer 18 and are oppositely disposed。Positive pole 10 is provided with positive electrode active material layer 14 on positive electrode collector 12。Negative pole 20 is provided with negative electrode active material layer 24 on negative electrode collector 22。Positive electrode active material layer 14 and negative electrode active material layer 24 are contacted with the both sides of barrier film 18 respectively。The end of positive electrode collector 12 and negative electrode collector 22 connects wire 60,62 respectively, and the end of wire 60,62 extends to the outside of casing 50。
Positive electrode collector 12 as positive pole 10 such as can use alumina foil etc.。Positive electrode active material layer 14 comprises above-mentioned active material particle 1, binding agent and the conductive material being added as needed on。White carbon black class, material with carbon element such as can be enumerated, the electroconductive oxide of ITO etc. as the conductive material being added as needed on。
As long as above-mentioned active material particle and conductive material can be bondd on the current collector all without particular limitation of, it is possible to use known binding agent by binding agent。For example, it is possible to enumerate the fluororesin of Kynoar (PVDF), politef (PTFE), vinylidene-hexafluoropropylene copolymer etc.。
Positive pole can make by known method, such as, electrode active material containing above-mentioned active material particle 1 or active material particle 1, binding agent and conductive material are made an addition to the solvent corresponding to its kind (such as when PVDF for N-Methyl pyrrolidone, N, dinethylformamide equal solvent) in be configured to slurry, this slurry is spread upon the surface of positive electrode collector 12, dry it is thus possible to manufacture。
As negative electrode collector 22, Copper Foil etc. can be used。It addition, as negative electrode active material layer 24, the material containing negative electrode active material, conductive material and binding agent can be used。It is not particularly limited as conductive material, material with carbon element, metal powder etc. can be used。As the binding agent used in negative pole, the fluororesin such as Kynoar (PVDF), politef (PTFE), fluorinated ethylene propylene copolymer (FEP) can be used。
As negative electrode active material, it is possible to enumerate and can form the metal of compound with lithium containing material with carbon element, Al, Si, Sn etc. such as graphite or difficult graphitized carbons, with SiO2、SnO2Deng the noncrystalline compound that oxide is main body, lithium titanate (Li4Ti5O12) etc. granule。
The manufacture method of negative pole 20, the same with the manufacture method of positive pole 10 modulates slurry, coats on collector body。
It is not particularly limited as electrolyte, for instance in the present embodiment, it is possible to use contain the electrolyte of lithium salts in organic solvent。As lithium salts, for instance LiPF can be used6、LiClO4、LiBF4Deng salt。It addition, these salt can be used alone one, it is also possible to and with two or more。
As organic solvent, for instance Allyl carbonate, ethylene carbonate and diethyl carbonate, dimethyl carbonate, Ethyl methyl carbonate etc. can be used。These organic solvents can be used alone, it is also possible to mixes two or more with arbitrary ratio and uses。
It addition, spacer 18 can use the stretched PTFE film by polyethylene, polypropylene or the individual layers of porous membrane being made up of polyolefin, laminated body and above-mentioned resin compound or the fabric nonwoven cloth being made up of at least one constituent material in cellulose, polyester and polypropylene。
Laminated body 30 and electrolyte are sealed therein by casing 50。As long as casing 50 can suppress electrolyte to be leaked to outside, suppression moisture etc. invades the material within lithium rechargeable battery 100 from outside all without special restriction。For example, it is possible to utilize metal composite thin film。
Wire 60 and 62 can be formed by the conductive material of aluminum etc.。
The active substance of the present invention is also used as the electrode material of the electrochemical element beyond lithium rechargeable battery。As such electrochemical element, such as, the electrochemical capacitors etc. such as the secondary cell beyond the lithium rechargeable battery of lithium metal secondary battery (anode uses the electrode containing composite particles of the present invention, and negative electrode uses lithium metal) etc. or lithium-ion capacitance can be enumerated。
Hereinafter, specifically describe the present invention further based on embodiment and comparative example, but the present invention is not limited in below example。
(embodiment 1)
In embodiment 1, lithium nickel composite oxide (Li is used as above-mentioned positive active material matrix material when making positive pole1.2Ni0.175Co0.10Mn0.525O2) second particle。Next solwution method is adopted to carry out the cladding to positive active material substrate material surface。First, prepare respectively iron nitrate aqueous solution and etc. the lithium hydroxide aqueous solution of molar concentration, wherein regulate concentration and make ferric nitrate 9 hydrate with LiFe5O8Conversion is 0.5wt% relative to positive active material matrix material。Above-mentioned active substance matrix material is put in lithium hydroxide aqueous solution, stirring, make mixed solution。Then, above-mentioned iron nitrate aqueous solution it is added dropwise in above-mentioned mixed solution and stirs, making presoma pile up at positive active material substrate material surface。Filter product and reclaim, at 600 DEG C, carrying out heat treatment 6 hours in atmosphere。Assert the layer of cladding on particle surface by TEM-diffraction pattern and EELS, result can confirm that and defines LiFe5O8。
[making of positive pole]
As embodiment 1, above-mentioned active substance, conductive auxiliary agent and the solvent containing binding agent are mixed, are modulated into positive pole coating。Positive pole coating is coated on collector body aluminium foil (thickness 20 μm) by doctor blade method, dry at 100 DEG C, calendering。Thus obtain the positive pole being made up of positive electrode active material layer and collector body。As electric conductor, employ white carbon black (Deuki Kagaku Kogyo Co., Ltd manufactures, DAB50) and graphite。As the solvent containing binding agent, employ the N-Methyl pyrrolidone (Kureha Kagaku Kogyo K.K. manufactures, KF7305) having dissolved PVDF。
[making of negative pole]
Use native graphite, only use white carbon black as conductive auxiliary agent, with the method modulation negative pole coating same with positive pole coating。By doctor blade method by negative pole coatings after collector body Copper Foil (thickness 16 μm) is upper, dry and rolling at 100 DEG C。Thus obtain the negative pole being made up of negative electrode active material layer and collector body。
[making of lithium rechargeable battery]
Ready-made positive pole, negative pole and spacer (micro-porous film of polyolefin) are cut into the size of regulation。In order to weld bringing-out, positive pole and negative pole leave the part of uncoated electrode coating。By positive pole, spacer, negative pole lamination in order。When lamination, in order to not allow positive pole, spacer, negative pole misplace, it is coated with a small amount of hot-melt adhesive (ethylene-methacrylic acid copolymer, EMAA) and is fixed。Positive pole, negative pole have been respectively welded the aluminium foil (wide 4mm, long 40mm, thickness 100 μm) as bringing-out and nickel foil (wide 4mm, long 40mm, thickness 100 μm) with ultrasound wave。The polypropylene (PP) carrying out grafting with anhydrous maleic acid is attached on this bringing-out and is heating and curing, and this is the sealing in order to improve bringing-out and exterior body。As the battery exterior body enclosing the obtained cell device of lamination positive pole, spacer, negative pole, use the aluminum laminated material being made up of pet layer, Al layer and PP layer。The thickness of pet layer is 12 μm, and the thickness of Al layer is は 40 μm, and the thickness of PP layer is 50 μm。Wherein, PET is polyethylene terephthalate, and PP is polypropylene。When making battery exterior body, PP layer is arranged on the inner side of exterior body。Loading cell device in exterior body and add electrolyte in right amount, vacuum seals exterior body, thus having made the lithium rechargeable battery of embodiment 1。In the mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC), the LiPF that concentration is 1M (mol/L) has been dissolved it addition, employ as electrolyte6Solution。In mixed solvent, the volume ratio of EC and DMC is EC:DMC=50:50。
The battery with nonaqueous electrolyte made according to the method described above is carried out under the following conditions the mensuration of charge/discharge cycle characteristics。It is 4.70V at upper voltage limit, after charging one hour when electric current 200mA, is 2.0V at final voltage, discharges when electric current is 200mA, and repeat this charge and discharge cycles 100 times (circulation experiment)。This experiment carries out at 30 DEG C。
With secondary discharge capacity for benchmark, circulation afterwards and circulate the discharge capacity obtained after 100 times to calculate its capability retention 50 times。
Discharge capacity/secondary discharge capacity × 100 (%) after capability retention=n circulation
N=50 time or 100 times circulation
(embodiment 2)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 1wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that the near surface of matrix material defines LiFe5O8。
(embodiment 3)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 2.5wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS in the same manner as in Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(embodiment 4)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 5wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(embodiment 5)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 10wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(embodiment 6)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 15wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(embodiment 7)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 17wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(embodiment 8)
Except when preparing lithium hydroxide aqueous solution and iron nitrate aqueous solution, adjusting concentration and make with LiFe5O8Being outside 20wt% relative to the positive active material finally given after conversion, all the other are all identical with embodiment 1。It addition, confirmed by TEM and EELS similarly to Example 1, it is possible to confirm that substrate material surface has been formed about LiFe5O8。
(comparative example 1)
Except as positive pole, not carrying out surface treatment, and only with beyond active substance, all the other be all identical with example 1。
(table 1)
In table 1, having the effect having carried out surface treatment in embodiment 1～7, this effect is for compared with comparative example 1, and the capability retention after circulating 50 times and circulating 100 times is high especially。Further, the amount of clad, in the scope of 1% to 15%, circulates the capability retention after 100 times and is positively retained at more than 80%。
(comparative example 2)
Use the method that patent documentation 1 is recorded, prepare sodium hydrate aqueous solution and manganese nitrate aqueous solution so that with Mn2O3It is scaled 2.5wt%, in sodium hydrate aqueous solution, puts into positive active material matrix material similarly to Example 1, and stir, obtain mixed solution。This mixed solution instills manganese nitrate, makes presoma be deposited in positive active material substrate material surface。Operation below is all identical with embodiment 1, defines the clad of manganese oxide。
(comparative example 3)
Use the method recorded in patent documentation 2, rotational flow groove is used to sparge on the positive active material matrix material identical with embodiment 1 using the sol solution as alumina precursor to pile up the aluminium oxide of the clad of 2.5wt% at positive active material substrate material surface。Operation afterwards is all identical with embodiment 1, defines the clad of aluminium oxide。
(table 2)
In table 2, embodiment 3 has carried out LiFe5O8The effect of surface treatment, this effect for compared with comparative example 2,3, circulate 50 times and to circulate the capability retention after 100 times high especially。
(embodiment 9)
LiFeO has been made in advance by solid phase method2Granule。The mode of lithium carbonate and ferrum oxide 1:1 in molar ratio is in harmonious proportion and mixes, burns till at 850 DEG C。The LiFeO of the electrochemicaUy inert that powder is cubic crystal rock salt structure obtained is determined by X-ray diffraction2。This powder is pulverized in ball mill, relative to the mode that positive active material matrix material is 0.5wt%, this powder of ormal weight is mixed with the positive active material matrix material used in embodiment 1 by the ratio of the clad finally given afterwards, ball mill has carried out surface treatment。At 600 DEG C, carry out the heat treatment of 6 hours afterwards further in atmosphere, make finish materials。Use this powder, make battery。The making of battery is identical with embodiment 1。
(embodiment 10)
Except the LiFeO that will make in embodiment 92Powder as clad and be 1wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 9。
(embodiment 11)
Except the LiFeO that will make in embodiment 92Powder as clad and be 2.5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside,
All the other are all identical with embodiment 9。
(embodiment 12)
Except the LiFeO that will make in embodiment 92Powder as clad and be 5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 9。
(embodiment 13)
Except the LiFeO that will make in embodiment 92Powder as clad and be 10wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 9。
(embodiment 14)
Except the LiFeO that will make in embodiment 92Powder as clad and be 15wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 9。
(embodiment 15)
Except the LiFeO that will make in embodiment 92Powder as clad and be 20wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 9。
(table 3)
In table 3, can confirm that the effect having carried out surface treatment in embodiment 9～15, the capability retention after circulating after 50 times and circulating 100 times is higher compared with comparative example 1。Particularly the amount of clad is in the scope of 1% to 15%, circulates the capability retention after 100 times and is maintained at more than 80%。
(embodiment 16)
LiFe has been made in advance by solid phase method5O8Granule。The mode of lithium carbonate and ferrum oxide 1:5 in molar ratio is in harmonious proportion and mixes, burns till at 850 DEG C。The LiFe that powder is spinel structure obtained is determined by X-ray diffraction5O8。This powder is pulverized with ball mill, relative to the mode that positive active material matrix material is 0.5wt%, this powder of ormal weight is mixed with the positive active material matrix material used in embodiment 1 by the ratio of the clad finally given afterwards, ball mill has carried out surface treatment。At 600 DEG C, carry out the heat treatment of 6 hours afterwards further in atmosphere, make finish materials。Use this powder, make battery。The making of battery is identical with embodiment 1。
(embodiment 17)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 1wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 18)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 2.5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 19)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 20)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 10wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 21)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 15wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 22)
Except the LiFe that will make in embodiment 165O8Powder as clad and be 20wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(table 4)
In table 4, can confirm that the effect having carried out surface treatment in embodiment 16～22, the capability retention after circulating after 50 times and circulating 100 times is higher compared with comparative example 1。Particularly the amount of clad is in the scope of 1% to 15%, circulates the capability retention after 100 times and is maintained at more than 80%。
(embodiment 23)
Li has been made in advance by solid phase method5FeO4Granule。The mode of lithium carbonate and ferrum oxide 5:1 in molar ratio is in harmonious proportion and mixes, burns till at 850 DEG C。Determined that by X-ray diffraction the powder obtained is Li5FeO4。This powder is pulverized with ball mill, relative to the mode that positive active material matrix material is 0.5wt%, this powder of ormal weight is mixed with the positive active material matrix material used in embodiment 1 by the ratio of the clad finally given afterwards, ball mill has carried out surface treatment。At 600 DEG C, carry out the heat treatment of 6 hours afterwards further in atmosphere, make finish materials。Use this powder, make battery。The making of battery is identical with embodiment 1。
(embodiment 24)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 1wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(embodiment 25)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 2.5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(embodiment 26)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(embodiment 27)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 10wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(embodiment 28)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 15wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(embodiment 29)
Except the Li that will make in embodiment 235FeO4Powder as clad and be 20wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 23。
(table 5)
In table 5, can confirm that the effect having carried out surface treatment in embodiment 23～29, the capability retention after circulating after 50 times and circulating 100 times is higher compared with comparative example 1。Particularly the amount of clad is in the scope of 1% to 15%, circulates the capability retention after 100 times and is maintained at more than 80%。
(embodiment 30)
Except weighing the LiFeO made in embodiment 92The LiFe made in granule and embodiment 165O8Granule becomes the ratio that weight is 50:50, and has been mixed to get mixed-powder with ball mill。Using this mixed-powder as clad and be 0.5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 16。
(embodiment 31)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 1wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(embodiment 32)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 2.5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(embodiment 33)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 5wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(embodiment 34)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 10wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(embodiment 35)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 15wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(embodiment 36)
Except the mixed-powder that will make in embodiment 30 is as clad, and be 20wt% relative to positive active material matrix material ormal weight mix with active substance matrix material outside, all the other are all identical with embodiment 30。
(table 6)
In table 6, can confirm that the effect having carried out surface treatment in embodiment 30～36, the capability retention after circulating after 50 times and circulating 100 times is higher compared with comparative example 1。Particularly the amount of clad is in the scope of 1% to 15%, circulates the capability retention after 100 times and is maintained at more than 80%。
Claims (5)
1. a positive active material, it is characterised in that
On positive active material matrix material, there is at least one of clad being coated with described positive active material matrix material,
Described positive active material matrix material has formula LiMO2Material and Li2MnO3The solid solution of represented lithium manganese oxide, wherein, the M in formula is more than one the metallic element in Co, Ni and Mn,
Described clad contains selected from rock salt LiFeO2、LiFe5O8、Li5FeO4In at least one。
2. positive active material as claimed in claim 1, it is characterised in that
Described clad is coated with the amount being 1～15wt% relative to described positive active material matrix material。
3. positive active material as claimed in claim 1 or 2, it is characterised in that
Described positive active material matrix material is the second particle that primary particle is aggregated into。
4. a positive pole, wherein,
Containing, for example the positive active material according to any one of claims 1 to 3。
5. a lithium rechargeable battery, wherein,
Possess: the positive pole with the positive active material according to any one of Claims 1 to 4, the negative pole with negative electrode active material and between as described in positive pole and as described in spacer between negative pole and nonaqueous electrolyte。
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