CN101223660A - Positive electrode active material and process for producing the same, and battery - Google Patents
Positive electrode active material and process for producing the same, and battery Download PDFInfo
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- CN101223660A CN101223660A CNA2006800262281A CN200680026228A CN101223660A CN 101223660 A CN101223660 A CN 101223660A CN A2006800262281 A CNA2006800262281 A CN A2006800262281A CN 200680026228 A CN200680026228 A CN 200680026228A CN 101223660 A CN101223660 A CN 101223660A
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- active material
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- composite xoide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
This invention provides a positive electrode active material, which can provide a high capacitance and, at the same time, can improve stability or low-temperature properties, and process for producing the same and a battery. A positive electrode (21) comprises a positive electrode active material that comprises a lithium composite oxide comprising Li and at least one element of Co, Ni and Mn and contains in its surface part P and at least one element of Ni, Co, Mn, Fe, Al, Mg and Zn as a covering element. Preferably, the content of the covering element is higher in the surface than in the inside and is reduced from the surface toward the inside.
Description
Technical field
The present invention relates to comprise the positive active material of lithium composite xoide, the manufacture method and the battery of this positive active material.
Background technology
In recent years, along with portable set such as notebook computer with mobile phone is meticulous further and multifunction, the energy consumption of described equipment increases day by day, and requires further to improve as the capacity of the battery of described device power supply (DPS).Wherein, with regard to cost benefit and reduce size and weight reduction with regard to, huge to the demand of secondary cell with higher capacity.As the battery that satisfies this requirement, enumerate for example lithium secondary battery.
As negative pole, its operating voltage is in 4.2V～2.5V scope as positive pole, material with carbon element for lithium secondary battery employing lithium and cobalt oxides commonly used at present.When lithium secondary battery was worked under maximum 4.2V, lithium secondary battery had only used about 60% of anodal used positive active material such as lithium and cobalt oxides theoretical capacity.Thereby, when further raising charging voltage, can use residual capacity in principle, in fact, known when charging voltage be 4.25V or when above, realized high energy density (referring to Patent Document 1).
Yet when charging voltage increased, positive electrode potential improved, thereby had strengthened near anodal oxidizing atmosphere, thereby electrolyte is easy to the deterioration by oxidation Decomposition.Therefore, degradation problem under for example efficiency for charge-discharge decline and the cycle characteristics appears.In addition, this reaction is at high temperature more violent, thereby exists and operate under the high temperature or the problem of the obvious deterioration of electrolyte when depositing secondary cell.In addition, in some cases, secondary cell for example uses under the cold climate at low temperature environment, thereby needs secondary cell all to have excellent characteristic under high temperature and low temperature.
For improving characteristic, in lithium composite xoide such as lithium and cobalt oxides, form for example aluminium (Al), magnesium (Mg) or titanium (Ti)) etc. the method for solid solution of element be known.In addition, as the technology of improving positive active material stability or low-temperature characteristics, be set forth in the method that forms coating film on the active material surface by stabilizing material.For example, patent documentation 2 has been described and has been utilized aluminium oxide (Al
2O
3) coating the surface of (coating) lithium and cobalt oxides, patent documentation 3 has been described on the surface of nickel/cobalt composite oxide and has been formed aluminous layer.In addition, patent documentation 4 has been described and has been utilized lithium titanate (LiTiO
2) coating the surface of lithium and cobalt oxides, patent documentation 5 and 6 has been described compound MXO
KThe formation method of the superficial layer that (M represents metal, and X represents to form with oxygen the element of two keys, k=2～4) makes.In addition, patent documentation 7 has been described the manganese concentration that the lip-deep manganese of lithium oxide (Mn) concentration is higher than lithium oxide inside, and patent documentation 8 has been described with sulfate and coated the lithium and cobalt oxides particle surface.
Patent documentation 1: international open No.WOO3/0197131
Patent documentation 2: the spy opens the 2001-143703 communique
Patent documentation 3: the spy opens the 2001-143708 communique
Patent documentation 4: the spy opens the 2004-103566 communique
Patent documentation 5: the spy opens the 2003-7299 communique
Patent documentation 6: the spy opens the 2003-331846 communique
Patent documentation 7: the spy opens the 2004-348981 communique
Patent documentation 8: the spy opens the 2003-20229 communique
Summary of the invention
Yet, in lithium composite xoide, form in the technology of element solid solution body such as aluminium for example, when the amount of solid solution is too small, cycle characteristics in the time of can not substantially improving high temperature or high charge voltage, when the amount of solid solution was excessive, charge/discharge capacity descended, thereby the raising cell voltage is nonsensical.In addition, only can not substantially improve characteristic, thereby need further to improve by the coating film of making at surface formation oxide.
For above-mentioned consideration, the purpose of this invention is to provide the positive active material that can obtain high power capacity and can improve stability or low-temperature characteristics, the manufacture method of described positive active material and battery.
Positive active material of the present invention comprises: lithium composite xoide, and it comprises lithium (Li) and is selected from least a in cobalt (Co), nickel (Ni) and the manganese (Mn); Phosphorus (P) and be selected from least a in nickel, cobalt, manganese, iron (Fe), aluminium (Al), magnesium (Mg) and the zinc (Zn) is as the lip-deep coating element of described lithium composite xoide.
Positive active material manufacture method of the present invention may further comprise the steps: utilize to comprise phosphorus and to be selected from compound at least a in nickel, cobalt, manganese, iron, aluminium, magnesium and the zinc lithium composite xoide microparticle surfaces is coated, described lithium composite xoide comprises lithium and is selected from least a in cobalt, nickel and the manganese; And they are carried out sintering.
Battery of the present invention comprises: positive pole; Negative pole; And electrolyte, the wherein anodal positive active material that comprises lithium composite xoide that comprises, described lithium composite xoide comprises lithium and is selected from least a in cobalt, nickel and the manganese, and positive active material comprises phosphorus and is selected from least a as its lip-deep coating element in nickel, cobalt, manganese, iron, aluminium, magnesium and the zinc.
In positive active material of the present invention, comprise lithium composite xoide, and on the surface of lithium composite xoide, comprise phosphorus and coat element, thereby can obtain high power capacity and can improve chemical stability and low-temperature characteristics.Therefore, in battery of the present invention, high energy density can be obtained, and high temperature or low temperature efficiency for charge-discharge can be improved.
In the manufacture method of positive active material of the present invention, utilization comprises phosphorus and is selected from compound at least a in nickel, cobalt, manganese, iron, aluminium, magnesium and the zinc, the lithium composite xoide particle surface is coated, and carry out sintering, thereby can easily obtain positive active material.
Description of drawings
Fig. 1 is the structure sectional view of first kind of secondary cell of the positive active material of use embodiment of the present invention.
Fig. 2 is the local amplification sectional view of the spiral winding electrode (spirally wound electrodebody) in the secondary cell shown in Figure 1.
Fig. 3 is the structure decomposition diagram of second kind of secondary cell of the positive active material of use embodiment of the present invention.
Fig. 4 is the sectional view along the spiral winding electrode of Fig. 3 center line I-I intercepting.
The element ratio of components variation diagram along embodiment 1-1 positive active material depth direction of Fig. 5 for recording by Auger electron spectroscopy.
Fig. 6 is for utilizing the X-ray diffraction spectrum of used positive active material among the embodiment 3-1 that CuK α radiation (Cuk α radiation) records.
Fig. 7 is the X-ray diffraction spectrum that utilizes used positive active material among the embodiment 3-2 that CuK α radiation records.
Fig. 8 is the X-ray diffraction spectrum that utilizes used positive active material among the comparative example 3-1 that CuK α radiation records.
The element ratio of components variation diagram along embodiment 5-1 positive active material depth direction of Fig. 9 for recording by Auger electron spectroscopy.
The element ratio of components variation diagram along embodiment 9-3 positive active material depth direction of Figure 10 for recording by Auger electron spectroscopy.
Embodiment
Below with reference to accompanying drawing preferred embodiment is described in detail.
The positive active material of embodiment of the present invention is for example particulate matter, and comprises that the core of lithium-contained composite oxide, described lithium composite xoide comprise lithium and be selected from least a in cobalt, nickel and the manganese.In addition, the superficial layer of inclusion compound is arranged at least a portion on core surface, described compound comprises phosphorus and is selected from least a in nickel, cobalt, manganese, iron, aluminium, magnesium and the zinc.In other words, positive active material comprises lithium composite xoide, and comprises phosphorus and be selected from least a as the lip-deep coating element of described lithium composite xoide in nickel, cobalt, manganese, iron, aluminium, magnesium and the zinc.Therefore, this positive active material can obtain high energy density and can improve chemical stability or low-temp reaction.
As lithium composite xoide, for example the compound of Chemical formula 1,2 or 3 expressions is preferred, and can comprise in the described compound two or more.This is because can obtain high energy density with this composition.
(Chemical formula 1)
Li
xCo
aM1
bO
2-c
(wherein M1 represents at least a in nickel, manganese, magnesium, aluminium, boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron, copper (Cu), zinc, molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr) and the silicon (Si), x, a, b and c value are respectively in following scope: 0.8≤x≤1.2,0.8≤a≤1,0≤b≤0.2 ,-0.1≤c≤0.2, M1 is to improve the element of stability etc. and is the arbitrary element that adds as required.)
(Chemical formula 2)
Li
yNi
dM2
eO
2-f
(wherein M2 represents to be selected from least a in cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium, tungsten, zirconium and the silicon, y, d, e and f value are respectively in following scope: 0.8≤y≤1.2,0.3≤d≤0.98,0.02≤e≤0.7 ,-0.1≤f≤0.2, M2 is to improve the element of stability etc. and is the arbitrary element that adds as required.)
(chemical formula 3)
Li
zMn
2-gM3
gO
4-h
(wherein M3 represents to be selected from least a in cobalt, nickel, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and the tungsten, z, g and h value are respectively in following scope: 0.8≤z≤1.2,0≤g＜1.0 and-0.2≤h≤0.2, M3 is to improve the element of stability etc. and is the arbitrary element that adds as required.)
Superficial layer also can comprise any other element except that comprising above-mentioned coating element.As other element, enumerate lithium, oxygen (O), constitute the element of lithium composite xoide etc.The compound that can comprise one or both or more kinds of formation superficial layers.As coating element, phosphorus and to be selected from least a in manganese, magnesium and the aluminium be preferred.This is because can obtain better characteristic.Comprising aluminium as the situation that coats element under, from the teeth outwards the atomic ratio of phosphorus and aluminium (P/Al) be preferably 0.3 or more than, more preferably in 0.35～12.7 scope, (comprise two-end-point).This is because when this atomic ratio is too small, can not obtain effect of sufficient, and when this atomic ratio was excessive, it was saturated to improve effect.
In addition, the lip-deep coating constituent content of positive active material is higher than the coating constituent content of positive active material inside, and existing coating element is reduced from the positive active material surface to positive active material inside.This is because can obtain better effect.With respect to the weight of the lithium composite xoide that is comprised in the core, the amount of superficial layer is preferably 0.2wt%～5wt% (comprising two-end-point).This be because, measure when too small when this, can not obtain effect of sufficient, and measure when excessive capacity decline when this.In addition, the preferred covering amount that coats element in the superficial layer depends on the kind that coats element, comprising under phosphorus and manganese the situation as the coating element, covering amount is preferably 0.2mol%～6.0mol% (comprising two-end-point) with respect to lithium composite xoide, under the situation that comprises phosphorus and magnesium, covering amount is preferably 0.2mol%～4.0mol% (comprising two-end-point).Perhaps, comprising under phosphorus and aluminium the situation, comprise that the total amount of the coating element of phosphorus and aluminium is 0.2mol%～6.0mol% (comprising two-end-point) with respect to lithium composite xoide as the coating element.This be because, in all cases, measure when too small when this, can not obtain effect of sufficient, and measure when excessive capacity decline when this.
Can come the decision table surface layer by constitute the change in concentration of element to its internal inspection positive active material from the positive active material surface.For example, in by attenuate positive active materials such as sputters, analyze the composition of positive active material, measure change in concentration by utilizing Auger electron spectroscopy (AES) or secondary ion mass spectrometry (SIMS) (SIMS).In addition, can be by positive active material slowly be dissolved in acid solution etc., and the positive active material by the dissolving of inductive couple plasma (ICP) analysis of spectrum is over time, measures change in concentration.
For example can following manufacturing positive active material: mix and the compound of sintering lithium composite xoide formation element, thereby form granular core; Described core is put into solution or the suspension that comprises the compound that coats element, comprise the surface that the compound that coats element coats described core with utilization; And the described compound of sintering, thereby form superficial layer.In addition, for example can following manufacturing positive active material: form core in an identical manner; Coat the surface of the compound coating core of element then by sputtering method, laser ablation method, mechanical fusion method (mechanofusion method) etc. utilizations; And the described compound of sintering.As core material and surface layer material, can use oxide, hydroxide, oxyhydroxide, carbonate, nitrate, organic complex salt of each element etc.
For example, positive active material is used for secondary cell as described below.
(first kind of secondary cell)
Fig. 1 shows the sectional view of the first kind of secondary cell that uses the present embodiment positive active material.Secondary cell is so-called lithium rechargeable battery, and wherein lithium inserts and deviate from capacity component (capacity component) the expression capacity of negative plates of lithium as the electrode reaction thing.This secondary cell is so-called cylinder type, and comprise the spiral winding electrode 20 that comprises a pair of bar shaped anodal 21 and bar shaped negative pole 22, this bar shaped anodal 21 and bar shaped negative pole 22 in the cylindrical battery shell 11 of basic hollow with between the two dividing plate 23 screw windings.To be injected in the battery case 11 as the electrolyte of liquid electrolyte, and utilize described electrolyte dipping dividing plate 23.Battery case 11 is made by for example nickel-clad iron, and a closed end of battery case 11 and the other end opening.In battery case 11, dispose a pair of insulation board 12 and 13, make spiral winding electrode 20 be clipped between described two insulation boards along direction perpendicular to peripheral coiling surface.
In the open end portion of battery case 11, by packing ring 17 calkings, battery cover 14 is installed and is placed relief valve mechanism 15 and ptc device (PTC device) 16 in the battery cover 14, and with the inner sealing of battery case 11.Battery cover 14 is by for example making with battery case 11 identical materials.Relief valve mechanism 15 is electrically connected on the battery cover 14 by PTC device 16, and work as because internal short-circuit or external heat, the interior pressure of battery increases to a certain degree or when higher, and disc plate 15A counter-rotating (flip) is to cut off being electrically connected between battery cover 14 and the spiral winding electrode 20.When temperature raise, PTC device 16 was by increased resistance restriction electric current, thereby prevented the abnormal heating that risen by high-current leading.Packing ring 17 is made by for example insulating material, and its surface scribbles pitch.
Center with centrepin 24 insertion spiral winding electrode 20.The positive wire of being made by aluminium etc. 25 links to each other with the positive pole 21 of spiral winding electrode 20, and the negative wire of being made by nickel etc. 26 links to each other with negative pole 22.Positive wire 25 is welded on the relief valve mechanism 15 so that be connected on the battery cover 14, and with negative wire 26 welding and be electrically connected on the battery case 11.
Fig. 2 shows the partial enlarged drawing of spiral winding electrode 20 shown in Figure 1.Anodal 21 have following structure: positive electrode active material layer 21B is configured in the both sides of the positive electrode collector 21A with a pair of apparent surface.Although do not illustrate, can be only at the side configuration positive electrode active material layer 21B of positive electrode collector 21A.Positive electrode collector 21A is made by for example metal forming such as aluminium foil, nickel foil or stainless steel foil.Positive electrode active material layer 21B comprises for example particulate positive electrode active material of the present embodiment, if needed, comprises for example graphite and binding agent polyvinylidene fluoride for example of electric conductor, and can comprise any other positive active material.
Negative electrode active material layer 22B comprises one or both or more kinds of negative material that can insert and deviate from lithium as negative electrode active material, and if necessary, comprise with positive electrode active material layer 21B in identical binding agent.
In secondary cell, therefore the charging capacity of negative material that can insert and deviate from lithium does not have lithium metal to separate out on the negative pole 22 in charging process greater than anodal 21 charging capacity.
In addition, under the state of charging fully, the open circuit voltage of secondary cell (being cell voltage) can be 4.20V, is higher than 4.20V and in 4.25V～4.60V scope (comprising two-end-point) but be preferably designed for.This be because, but energization density when improving cell voltage, according to the present embodiment, the chemical stability of positive active material is improved, even therefore improve cell voltage, also can obtain excellent cycle characteristics.In this case, be that the situation of 4.20V is compared with cell voltage, even use identical positive active material, also improved the lithium of per unit weight and deviate from amount, therefore can adjust the amount of positive active material and negative electrode active material in view of the above.
Negative material as inserting and deviate from lithium for example uses material with carbon element, but as difficult graphitized carbon graphitized carbon, graphite, RESEARCH OF PYROCARBON class, coke class, nature of glass carbon class, organic high molecular compound sintered body, carbon fiber and active carbon.Wherein, the coke class comprises pitch coke, needle coke, petroleum coke etc.The organic high molecular compound sintered body is for by at the polymer (for example phenolic resins and furane resins) of suitable sintering temperature carbonization, but and the part in this polymer sintered body can sort out awkward graphitized carbon or graphitized carbon.These material with carbon elements are preferred, and this is because changes of crystal is very little when discharging and recharging, and can obtain high charge/discharge capacity and excellent cycle characteristics.Especially, graphite is preferred, and this is because its electrochemical equivalent is big and can obtain high energy density.In addition, difficult graphitized carbon is preferred, and this is because can obtain excellent cycle characteristics.In addition, the material with carbon element that charging/discharging voltage is low, more specifically, charging/discharging voltage is preferred near the material with carbon element of lithium metal, this is because can easily improve the energy density of battery.
As the negative material that can insert and deviate from lithium, enumerate can insert and deviate from lithium and comprise being selected from least a material in metallic element and the metalloid element as element, this is because can obtain high energy density when using this material.Especially, described material more preferably uses with material with carbon element, and this is because can obtain high energy density and excellent cycle characteristics.Negative material can be simple substance, alloy or the compound of metallic element or metalloid element, perhaps comprises the material that comprises one or both or more kinds of phase in them to small part.In the present invention, alloy is meant the alloy that comprises two or more metallic elements and comprises one or more metallic elements and the alloy of one or more metalloid elements.In addition, alloy can comprise nonmetalloid.As alloy structure, enumerate solid solution, eutectic (eutectic mixture), intermetallic compound or the coexisting body of two or more wherein.
As metallic element contained in the negative material or metalloid element, enumerate magnesium, boron, aluminium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) or platinum (Pt).They can be crystallization or amorphous.
Wherein, as negative material, the negative material that comprises 4B family metallic element in the short period type periodic table of elements or 4B same clan metallic element is preferred, and comprises that at least a negative material as element is preferred in silicon and the tin.This is because silicon and tin have high insertion and deviates from the ability of lithium and can obtain high energy density.
As ashbury metal, enumerate and for example except that comprising tin, also comprise at least a alloy that is selected from silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb) and the chromium as second kind of element.As silicon alloy, enumerate and for example except that comprising silicon, also comprise at least a alloy that is selected from tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and the chromium as second kind of element.
As the compound of tin or the compound of silicon, enumerate the compound that for example comprises oxygen or carbon (C), and this compound also can comprise above-mentioned second kind of element except that comprising tin or silicon.
As the negative material that can insert and deviate from lithium, also enumerate other metallic compound or polymeric material.As metallic compound, enumerate oxide such as MnO
2, V
2O
5Or V
6O
13, sulfide such as NiS or MoS or nitride such as lithium nitride, as polymeric material, enumerate polyacetylene, polypyrrole etc.
Dividing plate 23 is made by for example synthetic resin (for example polytetrafluoroethylene, polypropylene or polyethylene) perforated membrane or porous ceramic film, and dividing plate 23 can have the structure of stacked two or more perforated membranes.Wherein, the perforated membrane that polyolefin is made is preferred, and this is because prevent the respond well of short circuit, and can be by the stability of the effect improving battery that opens circuit.
Electrolyte comprises the solvent of being made by for example nonaqueous solvents such as organic solvent and is dissolved in the electrolytic salt of this solvent.
As nonaqueous solvents, can use cyclic carbonate, for example ethylene carbonate ester or propylene glycol carbonate, and preferably use one of ethylene carbonate ester and propylene glycol carbonate, particularly their mixture.This is because can improve cycle characteristics.
As nonaqueous solvents, except that the ring-type carbonic ester, preferably mix and use linear carbonate, for example diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester or methyl-propyl carbonic ester.This is because can obtain high ionic conductivity.
As nonaqueous solvents, preferably also comprise 2,4-difluoroanisole or vinylene carbonate (vinylenecarbonate).This is that the 4-difluoroanisole can improve discharge capacity because of 2, and vinylene carbonate can improve cycle characteristics.Therefore, because can improve discharge capacity and cycle characteristics, so preferably mix and use them.
Except that above-mentioned material, as nonaqueous solvents, enumerate the carbonic acid butanediol ester, gamma-butyrolacton, gamma-valerolactone, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, methyl acetate, methyl propionate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, the 3-methoxypropionitrile, N, dinethylformamide, the N-methyl pyrrolidone, N-methyl azoles quinoline ketone (N-methyloxazolidinone), N, the N-dimethyl-imidazolinone (N, N-dimethylimidazolidinone), nitromethane, nitroethane, sulfolane, dimethyl sulfoxide (DMSO), trimethyl phosphate etc.
In some cases, it is preferred replacing the compound that at least a portion hydrogen (H) forms in the nonaqueous solvents with fluorine (F), and this is because can improve the invertibity of electrode reaction according to the kind of electrode.
As electrolytic salt, enumerate for example lithium salts, and can only use a kind of lithium salts or use the mixture of two or more lithium salts.As lithium salts, enumerate LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiC (SO
2CF
3)
3, LiAlCl
4, LiSiF
6, LiCl, difluoro [oxalic acid-O, O '] lithium borate (difluoro[oxalate-O, O '] lithium borate, two (oxalate closes) lithium borate, LiBr etc.Wherein, LiPF
6Be preferred, this is because can obtain high ionic conductivity and improve cycle characteristics.
For example, can make secondary cell by following steps.
At first, for example, on positive electrode collector 21A, form positive electrode active material layer 21B, thereby form anodal 21.Following formation positive electrode active material layer 21B: mixed cathode active material, electric conductor and binding agent, thus form cathode mix; Described cathode mix is dispersed in solvent such as the N-N-methyl-2-2-pyrrolidone N-, thereby forms pasty state cathode mix slurry; Described cathode mix slurry is applied over positive electrode collector 21A; Dry solvent; And described cathode mix slurry is carried out compression moulding by roller mill etc.
In addition, for example, on negative electrode collector 22A, form negative electrode active material layer 22B, thereby form negative pole 22.Can or be selected from the combination of two or more methods in the said method by any method in for example vapor phase method, liquid phase method, sintering process or the cladding process, form negative electrode active material layer 22B.Forming under the situation of negative electrode active material layer 22B by vapor phase method, liquid phase method or sintering process, during formation, can make negative electrode active material layer 22B and negative electrode collector 22A at least a portion place alloying at interface between the two; Yet, can make their further alloyings by under vacuum atmosphere or nonoxidizing atmosphere, heat-treating.
As vapor phase method, for example can adopt physical deposition method or chemical deposition, more specifically, can adopt vacuum deposition method, sputtering method, ion plating method, laser ablation method, hot CVD (chemical vapour deposition (CVD)) method, plasma CVD method etc.As liquid phase method, can adopt known method, for example electroplate or chemical plating.As sintering process, can adopt known technology, for example normal pressure-sintered method (atmoshphere firingmethod), reaction sintering or hot pressing sintering method.Under situation about applying, can form negative pole 22 according to anodal 21 situation.
Then, wait by welding positive wire 25 is attached to positive electrode collector 21A, and negative wire 26 is attached to negative electrode collector 22A by welding etc.Subsequently, make anodal 21 and negative pole 22 with between the two dividing plate 23 screw windings, and an end of positive wire 25 is welded on the relief valve mechanism 15, one end of negative wire 26 is welded on the battery case 11, and the positive pole 21 of screw winding and negative pole 22 are clipped between a pair of insulation board 12 and 13, and are contained in the battery case 11.After being contained in positive pole 21 and negative pole 22 in the battery case 11, inject the electrolyte into battery case 11, with electrolyte dipping dividing plate 23.Subsequently, by packing ring 17 calkings, battery cover 14, relief valve mechanism 15 and PTC device 16 are fixed in the open end portion of battery case 11.Thereby form secondary cell illustrated in figures 1 and 2.
When to secondary cell charge, for example, lithium ion is deviate from from positive electrode active material layer 21B, and inserts negative material through electrolyte, and this negative material can insert and deviate to be included in lithium among the negative electrode active material layer 22B.Then, when secondary cell is discharged, for example, insert the lithium ion of negative electrode active material and deviate from and process electrolyte insertion positive electrode active material layer 21B, described negative electrode active material can insert and deviate from the lithium among the negative electrode active material layer 22B.In this embodiment, use comprises the positive active material of lithium composite xoide and the lip-deep coating element of lithium composite xoide, thereby improve anodal 21 chemical stability, even and improve the open circuit voltage under the complete charged state or at high temperature secondary cell charged, also can avoid anodal 21 with the deterioration reaction of electrolyte.In addition, can improve low-temp reaction.
Therefore, in this embodiment, comprise lithium composite xoide, and on the lithium composite xoide surface, comprise the coating element, thereby can improve the chemical stability of positive active material, and can avoid the capacity of positive active material under high voltage or the hot environment to descend.Thereby, even charging voltage is higher than 4.2V or at high temperature uses or deposit secondary cell, also can avoid the deterioration reaction of positive pole 21 and electrolyte, and can obtain high energy density, and can be by improving charge-discharge improved efficiency battery behavior such as cycle characteristics.In addition, can improve low-temp reaction and low-temperature characteristics.
(second kind of secondary cell)
Fig. 3 shows the structure of second kind of secondary cell of the present invention.In this secondary cell, the spiral winding electrode 30 that is attached with positive wire 31 and negative wire 32 on it is contained in the membranaceous packing component 40, thus can reduce this secondary cell size, alleviate its weight and dwindle its profile.
For example positive wire 31 and negative wire 32 are led to the outside from the inside of packing component 40 along identical direction.Positive wire 31 and negative wire 32 are made by for example sheet or net metal material such as aluminium, copper, nickel or stainless steel.
In addition, packing component 40 can for example polypropylene or metal film replace above-mentioned aluminium lamination press mold to make by the laminated film with any other structure, polymer film.
Fig. 4 shows along the sectional view of the spiral winding electrode 30 of Fig. 3 line I-I intercepting.Spiral winding electrode 30 be comprise anodal 33 and the screw winding layered product of negative pole 34, described anodal 33 and negative pole 34 between have dividing plate 35 and dielectric substrate 36, and protect the most external of these spiral winding electrode 30 with boundary belt 37.
For example, can make secondary cell by following steps.
At first, after the situation according to first kind of secondary cell forms positive pole 33 and negative pole 34, apply positive pole 33 and negative pole 34, and make this mixed solvent volatilization, formation dielectric substrate 36 by using the precursor solution that comprises electrolyte, macromolecular compound and mixed solvent.Subsequently, positive wire 31 is attached to positive electrode collector 33A, negative wire 32 is attached to negative electrode collector 34A.Then; form after the layered product being formed with the positive pole 33 of dielectric substrate 36 on it and being formed with the negative pole 34 of dielectric substrate 36 and therebetween dividing plate 35 laminations on it; this layered product of screw winding longitudinally; and boundary belt 37 adhered to the most external of this layered product, thereby form spiral winding electrode 30.At last, for example, this spiral winding electrode 30 is clipped between the packing component 40, and by thermal welding etc. that the marginal portion of packing component 40 is adhering to each other, thus this spiral winding electrode 30 is sealed in the packing component 40.At this moment, adhesive film 41 is inserted between positive wire 31, negative wire 32 and the packing component 30.Thereby, finish the secondary cell shown in Fig. 3 and 4.
In addition, can form secondary cell by following steps.At first; form positive pole 33 and negative pole 34 as mentioned above; and with positive wire 31 and negative wire 32 be attached to respectively anodal 33 and negative pole 34 after; to anodal 33 and negative pole 34 and the dividing plate between them 35 carry out lamination; thereby formation layered product; and this layered product of screw winding, then boundary belt 37 is adhered to the most external of this screw winding layered product, thereby form the precursor of screw winding body as spiral winding electrode 30.Then, this screw winding body is clipped between the packing component 40, and, encapsulates with the shape pouch, thereby the screw winding body is contained in the packing component 40 by the marginal portion that thermal welding adhere to remove the packing component 40 the marginal portion on one side.Then, be injected into electrolyte composition in the packing component 40 and seal the opening portion of this packing component 40, described electrolyte composition comprises the monomer and the polymerization initiator of electrolyte, macromolecular compound material, and also comprises any other material, for example polymerization inhibitor if necessary.Subsequently, make monomer polymerization with the formation macromolecular compound by heating, thereby form gel electrolyte layer 36, and the secondary cell shown in installation diagram 3 and 4.
The function of this secondary cell is identical with the function and the effect of first kind of secondary cell with effect.
Embodiment
Below will describe in detail specific embodiments of the invention.
(embodiment 1-1～1-5)
Form positive active material by following steps.At first, with commercially available reagent lithium carbonate (Li
2CO
3), cobalt carbonate (CoCO
3), aluminium hydroxide (Al (OH)
3) and magnesium carbonate (MgCO
3) mix, in ball mill, they are ground simultaneously.At this moment, the mol ratio of lithium, cobalt, aluminium and magnesium is Li: Co: Al: Mg=1.05: 0.98: 0.01: 0.01.Then, in 650 ℃ in air after this mixture of pre-burning 5 hours, in 950 ℃ of insulations 20 hours in air, the speed cooling by with 7 ℃ of per minutes is cooled to 150 ℃ with this mixing, thereby synthesizes lithium composite xoide.Subsequently, this lithium composite xoide is taken out to room temperature environment, and it is ground, thereby make this lithium composite xoide form granular lithium composite xoide, and this lithium composite xoide is used as core.When measuring the particle diameter of formed core by laser scattering method, average grain diameter is 13 μ m, and the assay value of the average chemical composition of lithium composite xoide is Li
1.03Co
0.98Al
0.01Mg
0.01O
2
Then, on the surface of core, form the superficial layer that comprises phosphorus-containing compound.At this moment, in embodiment 1-1, be dissolved in the formed solution of pure water, add 1kg as the lithium composite xoide particle of core and stir, 21.1g diammonium hydrogen phosphate ((NH to the 23.5g aluctyl
4)
2HPO
4) be dissolved in the solution that the formed solution of pure water splashes into the lithium-contained composite oxide particle and stir about 1 hour, thereby form solidliquid mixture, after this in 200 ℃ of these solidliquid mixtures of drying, and in 800 ℃ of heating 5 hours, thereby form superficial layer.
In embodiment 1-2, at 59.8g magnesium nitrate hexahydrate (Mg (NO
3)
26H
2O) be dissolved in the formed solution of pure water, add 1kg as the lithium composite xoide particle of core and stir, be dissolved in the 18.0g diammonium hydrogen phosphate in the solution that the formed solution of pure water splashes into the lithium-contained composite oxide particle and stir about 1 hour, thereby formation solidliquid mixture, after this in 200 ℃ of these solidliquid mixtures of drying, and in 800 ℃ of heating 5 hours, thereby form superficial layer.
In embodiment 1-3, pass through ball-milling method, in as the pure water of decentralized medium, grind 28.4g eight hypophosphite monohydrate cobalts, thereby form slurry (containing the solid portion that average grain diameter is 0.9 μ m), after this, in this slurry, add 1kg as the lithium composite xoide particle of core and stir, thereby form solidliquid mixture, and in 200 ℃ of these solidliquid mixtures of drying, in 800 ℃ of heating 5 hours, thereby form superficial layer.
In embodiment 1-4, mix 4.8g lithium phosphate and 18.6g Zinc phosphate tetrahydrate, and grind in the pure water as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.8 μ m), after this, in this slurry, add 1kg as the lithium composite xoide particle of core and stir, thereby form solidliquid mixture, and in 200 ℃ of these solidliquid mixtures of drying, in 800 ℃ of heating 5 hours, thereby form superficial layer.
In embodiment 1-5, mixed phosphate lithium, eight hypophosphite monohydrate manganese (Mn
3(PO
4)
28H
2O) and eight hypophosphite monohydrate iron (Fe
3(PO
4)
28H
2O), and in nitrogen current, carry out sintering in 550 ℃, thus synthetic LiMn
0.65Fe
0.35PO
4, after this, by mechanical fusion method LiMn
0.65Fe
0.35PO
4Coating is as the surface of the lithium composite xoide of core, thus the formation superficial layer.As LiMn to being synthesized
0.65Fe
0.35PO
4When carrying out the X-ray diffraction measurement, determine LiMn
0.65Fe
0.35PO
4Has olivine structural.
Positive active material to formed embodiment 1-1～1-5 carries out the powder x-ray diffraction measurement.As X-ray diffractometer, adopt rotary anode type X-ray diffractometer Rigaku RINT2500.X-ray diffractometer comprises that radius is the vertical goniometer of 185mm, and by the combination multichannel analyser with do not use colour filter such as the counting monochromator of K/3 colour filter makes that X ray is monochromatic to be composed.In measurement, as concrete X ray, adopt CuK α radiation (40kV, 200mA), and with the incidence angle DS of sample surfaces and the angle RS of diffracted ray and sample surfaces be 1 °, the width S S of entrance slit is 0.15mm, and adopt bounce technique by continuous sweep (sweep limits 2 θ=10 °～90 °, sweep speed be 4 °/mm) measure.
Thereby, in embodiment 1-1, the diffraction maximum of the lithium composite xoide that in core, comprises, also observe the diffraction maximum that comes from aluminium-phosphorus key.In embodiment 1-2, observe the diffraction maximum that comes from magnesium-phosphorus key.In embodiment 1-3, observe the diffraction maximum that comes from cobalt-phosphorus key.In embodiment 1-4, observe the diffraction maximum that comes from zinc-phosphorus key.In embodiment 1-5, observe the diffraction maximum that comes from manganese-phosphorus key and iron-phosphorus key.
In addition, formed each positive active material among embodiment 1-1～1-5 is adhered to the metal indium foil, by being used in combination Auger electron spectroscopy (AES) and sputter etching, the elemental composition of surface measurements and the element of depth direction distribute.Fig. 5 shows that the result of embodiment 1-1 is as representative.As phosphorus, aluminium, cobalt and the oxygen of essential element as shown in Figure 5.In addition, the element that is comprised in the superficial layer of each embodiment is as shown in table 1.Thereby, as shown in Figure 5, can determine in the superficial layer of each embodiment, all to exist phosphorus.In addition, find that the lip-deep coating element of positive active material (for example phosphorus and aluminium) content is higher than the coating constituent content in the positive active material inside, and described content changes continuously from the surface to inside, inwardly there is phosphorus in the degree of depth to about 150nm from the surface.
Then, use formed positive active material to form the secondary cell shown in Fig. 1 and 2.At first, according to positive active material: the weight ratio of lithium carbonate=95: 5, mix formed positive electrode active material powder and lithium carbonate powder, thereby formation mixture, according to mixture: the amorphous carbon dust: the weight ratio of polyvinylidene fluoride=94: 3: 3, mix this mixture, as the amorphous carbon dust of electric conductor (cut late black (ketjenblack)) with as the polyvinylidene fluoride of binding agent, thereby form cathode mix.Then, this cathode mix is dispersed in the N-N-methyl-2-2-pyrrolidone N-as solvent, thereby form the cathode mix slurry, and this cathode mix slurry evenly is applied in the both sides of the positive electrode collector 21A that the bar shaped aluminium foil of thick 20 μ m makes, dry this cathode mix slurry, and carry out compression moulding by roller mill, forming positive electrode active material layer 21B, thereby form anodal 21.Subsequently, aluminum positive wire 25 is attached to the end of positive electrode collector 21A.
In addition, according to powdered graphite: the weight ratio of polyvinylidene fluoride=90: 10, mix average grain diameter as negative electrode active material and be the spherical graphite powder of 30 μ m and as the polyvinylidene fluoride of binding agent, thereby form the negative pole mixture.Then, this negative pole mixture is dispersed in the N-N-methyl-2-2-pyrrolidone N-as solvent, thereby form the negative pole mixture paste, this negative pole mixture paste evenly is applied in the both sides of the negative electrode collector 22A that the bar shaped Copper Foil of thick 15 μ m makes, and carry out hot-forming to this negative pole mixture paste, with formation negative electrode active material layer 22B, thereby form negative pole 22.Subsequently, nickel system negative wire 26 is attached to the end of negative electrode collector 22A.At this moment, adjust and design the amount of positive active material and negative electrode active material, make that open circuit voltage is 4.40V under the state of charging fully, and represent the capacity of negative pole 22 by the capacity component of inserting and extracting out lithium.
Form after positive pole 21 and the negative pole 22, make microporosity separator 23, order lamination negative pole 22, dividing plate 23, positive pole 21 and dividing plate 23, thus form layered product, and several circles of this layered product of screw winding, freeze roll shape (jelly-roll type) spiral winding electrode 20 thereby form.
After spiral winding electrode 20 forms, it is clipped between a pair of insulation board 12 and 13, and negative wire 26 is welded on the battery case 11, positive wire 25 is welded on the relief valve mechanism 15, thereby this spiral winding electrode 20 is contained in the battery case 11 that nickel-clad iron makes.Subsequently, by depressurized system, 4.0g electrolyte is injected battery case 11.As electrolyte, use LiPF as the 1.0mol/kg of electrolytic salt
6Be dissolved in the electrolyte that solvent forms, the following formation of described solvent: according to the ethylene carbonate ester: dimethyl carbonate: weight ratio mixed carbonic acid glycol ester, dimethyl carbonate and the vinylene carbonate of vinylene carbonate=35: 64: 1.
Inject the electrolyte into after the battery case 11, carry out calking,, thereby obtain the cylindrical secondary battery that external diameter is 18mm, high 65mm with fixedly relief valve mechanism 15, PTC device 16 and battery cover 14 by 17 pairs of battery cases of packing ring 11.
In addition, as the comparative example 1-1 with respect to embodiment 1-1～1-5, form secondary cell according to the mode of embodiment 1-1～1-5, different is that former state is used lithium composite xoide (the average chemical composition Li that is used for core among embodiment 1-1～1-5
1.03Co
0.98Al
0.01Mg
0.01O
2) and do not form superficial layer.
1-2 as a comparative example forms secondary cell according to the mode of embodiment 1-1～1-5, and that different is lithium composite xoide (the average chemical composition Li that will be used for core among embodiment 1-1～1-5
1.03Co
0.98Al
0.01Mg
0.01O
2) with embodiment 1-5 in be used for the phosphorus-containing compound (LiMn of superficial layer
0.65Fe
0.35PO
4) mixture (according to lithium composite xoide: the weight ratio of phosphorus-containing compound=98: 2) as positive active material.
1-3 as a comparative example forms secondary cell according to the mode of embodiment 1-1～1-5, and different is, at 110.5g ANN aluminium nitrate nonahydrate (Al (NO
3)
39H
2O) be dissolved in the formed solution of pure water, add 1kg is used for core in embodiment 1-1～1-5 lithium composite xoide particle, and stir about 1 hour, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and,, thereby form positive active material with the formation superficial layer in 800 ℃ of heating 5 hours.
The secondary cell that forms among embodiment 1-1～1-5 and the comparative example 1-1～1-3 is discharged and recharged, to determine their rated capacity and cycle characteristics.Under the constant current of 2000mA, secondary cell is charged after cell voltage reaches 4.4V in 23 ℃, total charging interval reaches 3 hours under constant voltage under the constant voltage this secondary cell being charged, thereby secondary cell is charged fully.Under the constant current of 2000mA, secondary cell discharged and reach 2.75V, thereby secondary cell is discharged fully up to cell voltage in 23 ℃.Repeat this charge and discharge cycles, the discharge capacity of circulation 2 times the time is called rated capacity.In addition, as cycle characteristics, by (circulate 200 times time discharge capacity/rated capacity) * 100, the discharge capacity when determining circulation 200 times and the ratio of rated capacity.The gained result is as shown in table 1.
Table 1
| Lithium composite xoide in the core | The element that comprises in the superficial layer | Charging voltage (V) | Rated capacity (Wh) | Discharge capacitance (%) | |
| Embodiment 1-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | Al，Co，O，P | 4.4 | 9.01 | 91 |
| Embodiment 1-2 | Mg，Co，O，P | 8.99 | 92 | ||
| Embodiment 1-3 | Co，O，P | 9.00 | 91 | ||
| Embodiment 1-4 | Zn，O，P | 8.81 | 92 | ||
| Embodiment 1-5 | Mn，Fe，O，P | 8.85 | 91 | ||
| Comparative example 1-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | 4.4 | 9.17 | 80 |
| Comparative example 1-2 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 LiMn 0.65Fe 0.35PO 4 | - | 9.03 | 83 | |
| Comparative example 1-3 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | Al，Co，O | 9.01 | 88 |
As shown in table 1, in positive active material, dispose among the embodiment 1-1～1-5 of superficial layer, also only do not use the comparative example 1-1 of core to compare with wherein there being the allocation list surface layer, because the existence of superficial layer has caused the surface layer part of rated capacity to reduce; Yet, can substantially improve discharge capacitance.On the other hand, in the simple comparative example 1-2 that mixes of lithium composite xoide and phosphorus-containing compound, can improve discharge capacitance, but compare the degree of improvement with embodiment 1-1～1-5 little.In addition, in disposing the comparative example 1-3 that contains the superficial layer that aluminum oxide makes, discharge capacitance can not be substantially improved to being higher than 90%.
In other words,, dispose in use under the situation of positive active material of phosphorous superficial layer, still can obtain high energy density and can improve cycle characteristics even find that the open circuit voltage under the charged state fully is 4.25V or higher.
(embodiment 2-1～2-3)
Form positive active material by following steps.At first, mix nickelous sulfate, cobaltous sulfate and manganese sulfate with the solution form, thereby formation mixture, and ammoniacal liquor and sodium hydroxide solution are splashed into this mixture while stirring, thereby form nickel-cobalt-manganese composite hydroxide, described nickel-cobalt-manganese composite hydroxide is mixed with lithium hydroxide, thereby form mixture, in Oxygen Flow in 900 ℃ of heating this mixtures 10 hours, thereby synthetic nickel-cobalt-manganese composite oxide.When analyzing the sintered body of gained by the atom absorption spectra, this sintered body consist of Li
1.02Ni
0.1Co
0.8Mn
0.1O
2In addition, LiCoO among nickel-cobalt-manganese composite oxide and JCPDS (meeting of powder diffraction standard association) the file card No.50-0653
2Collection of illustrative plates identical, therefore can determine that nickel-cobalt-manganese composite oxide forms and LiCoO
2Identical bedded salt structure.Then, with nickel-cobalt-manganese composite oxide grind into powder, and nickel-cobalt-manganese composite oxide powder is last as core.When measuring the particle diameter of formed core by laser diffractometry, average grain diameter is 13 μ m.In addition, when observing powder by scanning electron microscopy (SEM), observing wherein reunites, and diameter is arranged is the spheroidal particle of the primary particle of 0.1 μ m～5 μ m.
Then, on core, form superficial layer.At this moment, in embodiment 2-1, mix 5g lithium phosphate (Li
3PO
4) and 21.8g eight hypophosphite monohydrate cobalt (Co
3(PO
4)
28H
2O), and in pure water, grind as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.8 μ m), after this, in this slurry, add 1kg as the lithium composite xoide particle of core and stir, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 800 ℃ of heating 5 hours, thereby superficial layer formed.
In embodiment 2-2, mix 5.3g one hydronium(ion) oxidation lithium (LiOHH
2O), 11.8g nickel hydroxide (Ni (OH)
2) and 17.1g diammonium hydrogen phosphate ((NH
4)
2HPO
4), and in pure water, grind as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.8 μ m), after this, in this slurry, add 1kg as the lithium composite xoide particle of core and stir, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 800 ℃ of heating 5 hours, thereby superficial layer formed.
In embodiment 2-3, mix 9.7g lithium phosphate (Li
3PO
4) and 33.3g eight hypophosphite monohydrate magnesium (Mg
3(PO
4)
28H
2O), and in pure water, grind as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.8 μ m), after this, in this slurry, add 1kg as the lithium composite xoide particle of core and stir, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 800 ℃ of heating 5 hours, thereby superficial layer formed.
When analyzing among embodiment 2-1～2-3 formed positive active material according to the mode of embodiment 1-1～1-5, can determine in superficial layer, to exist phosphorus-containing compound.Subsequently, according to the mode of embodiment 1-1～1-5, use formed positive active material to form secondary cell.
In addition, as comparative example 2-1～2-3 with respect to embodiment 2-1～2-3, mode according to embodiment 2-1～2-3 forms secondary cell, and former state that different is is used and is used for the lithium composite xoide particle of core among embodiment 2-1～2-3 and do not form superficial layer.
In addition, 2-4 as a comparative example forms secondary cell according to the mode of embodiment 2-1～2-3, and that different is the lithium composite xoide (Li that is used for core among embodiment 2-1～2-3
1.02Ni
0.1Co
0.8Mn
0.1O
2) and phosphorus-containing compound (LiMgPO
4) mixture (according to lithium composite xoide: the weight ratio of phosphorus-containing compound=97: 3) as positive active material.At this moment, following formation phosphorus-containing compound: according to 1: 1 mixed phosphate lithium of mol ratio (Li
3PO
4) and eight hypophosphite monohydrate magnesium Mg
3(PO
4)
28H
2O, thus mixture formed, in as the pure water of decentralized medium, grind this mixture by ball-milling method, in 200 ℃ this mixture is carried out drying, and heated these mixtures 5 hours in 800 ℃.When the phosphorus-containing compound to gained carries out the X-ray diffraction measurement, can determine that this phosphorus-containing compound is an olivine structural.
According to the mode of embodiment 1-1～1-5, the secondary cell that forms among embodiment 2-1～2-3 and the comparative example 2-1～2-4 is discharged and recharged, different is to change charging voltage, thereby determine the rated capacity and the cycle characteristics of secondary cell.Charging voltage is 4.4V in embodiment 2-1 and comparative example 2-1, is 4.5V in embodiment 2-2 and comparative example 2-2, is 4.6V in embodiment 2-3 and comparative example 2-3,2-4.The gained result is as shown in table 2.
Table 2
| Lithium composite xoide in the core | The element that comprises in the superficial layer | Charging voltage (V) | Rated capacity (Wh) | Discharge capacitance (%) | |
| Embodiment 2-1 | Li 1.02Ni 0.1Co 0.8Mn 0.1O 2 | Co，O，P | 4.4 | 8.93 | 91 |
| Embodiment 2-2 | Ni，O，P | 4.5 | 9.63 | 88 | |
| Embodiment 2-3 | Mg，O，P | 4.6 | 10.01 | 86 | |
| Comparative example 2-1 | Li 1.02Ni 0.1Co 0.8Mn 0.1O 2 | - | 4.4 | 9.03 | 81 |
| Comparative example 2-2 | - | 4.5 | 9.75 | 52 | |
| Comparative example 2-3 | - | 4.6 | 10.18 | 32 | |
| Comparative example 2-4 | Li 1.02Ni 0.1Co 0.8Mn 0.1O 2 LiMgPO 4 | - | 4.6 | 9.98 | 32 |
As shown in table 2, in positive active material, dispose among the embodiment 2-1～2-3 of superficial layer, only do not use the comparative example 2-1～2-3 of core to compare with there being the allocation list surface layer, can substantially improve discharge capacitance.Particularly, charging voltage is high more, and effect is big more.On the other hand, in the comparative example 2-4 of simple mixing lithium composite xoide and phosphorus-containing compound, when improving charging voltage, can not improve discharge capacitance.
In other words, even find open circuit voltage under the state of charging fully be 4.25V or more than, when the positive active material of phosphorous superficial layer is disposed in use, still can obtain high energy density and improve cycle characteristics, and open circuit voltage is high more, and obtainable effect is big more.
Embodiment 3-1～3-9, comparative example 3-1,3-2
Form positive active material by following steps.At first, evenly mix cobalt compound Co
3O
4With lithium salts Li
2CO
3, the mol ratio that makes lithium and cobalt is Li: Co=1.05: 1.Then, in air in 900 ℃ of heating said mixtures 5 hours, thereby form lithium and cobalt oxides (LiCoO
2).When according to the mode of embodiment 1-1～1-5 to lithium and cobalt oxides (LiCoO
2) carry out powder x-ray diffraction when measuring, listed lithium and cobalt oxides (LiCoO in the diffraction spectra peak of lithium and cobalt oxides and the JCPDS archives
2) the peak very mate.Then, to lithium cobalt composite oxide (LiCoO
2) pulverize, particle diameter is the powder of 14 μ m with regard to 50% accumulated size (cumulativesize) thereby form.
Then, the compound with phosphorus and aluminium is configured in lithium and cobalt oxides (LiCoO
2) the surface on.At this moment, in embodiment 3-1, the 34.9g aluctyl is dissolved in the 1L pure water, adds 1kg lithium and cobalt oxides (LiCoO
2) and stir, thereby form solution.Then, the 15.7g diammonium hydrogen phosphate is dissolved in the formed mixture of pure water is added drop-wise in this solution, stirred this solution more about 1 hour, thereby form solidliquid mixture.Formed solidliquid mixture is carried out drying, and in 700 ℃ of heating 10 hours, thereby positive active material formed.
In embodiment 3-2, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 23.3g, the amount of diammonium hydrogen phosphate is 20.9g.
In embodiment 3-3, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 17.4g, the amount of diammonium hydrogen phosphate is 23.5g.
In embodiment 3-4, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 11.6g, the amount of diammonium hydrogen phosphate is 26.1g.
In embodiment 3-5, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 4.36g, the amount of diammonium hydrogen phosphate is 29.4g.
In embodiment 3-6, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 2.44g, the amount of diammonium hydrogen phosphate is 1.09g.
In embodiment 3-7, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 4.88g, the amount of diammonium hydrogen phosphate is 2.19g.
In embodiment 3-8, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 75.4g, the amount of diammonium hydrogen phosphate is 33.8g.
In embodiment 3-9, form positive active material according to the mode of embodiment 3-1, the amount of different is aluctyl is 101.5g, the amount of diammonium hydrogen phosphate is 45.6g.
As comparative example 3-1 with respect to embodiment 3-1～3-9, form positive active material according to the mode of embodiment 3-1～3-9, different is not use aluctyl and diammonium hydrogen phosphate, but with lithium composite xoide (Li
1.03Co
0.98Al
0.01Mg
0.01O
2) be blended in the pure water.In addition, 3-2 as a comparative example forms positive active material according to the mode of embodiment 3-1～3-9, and different is not use aluctyl, and only uses the 31.3g diammonium hydrogen phosphate.
According to the mode of embodiment 1-1～1-5, the positive active material of embodiment 3-1 and 3-2 and comparative example 3-1 is carried out powder x-ray diffraction measure.The result is shown in Fig. 6,7 and 8.Thereby find, except that the diffraction maximum of the positive active material of comparative example 3-1 shown in Figure 8, in adopting the alpha-emitting diffraction spectra of CuK, the positive active material of Fig. 6 and 7 illustrated embodiment 3-1 and 3-2 has the diffraction maximum that is positioned at 22 °～22.5 °, 23 °～23.5 ° and 24.5 °～25 °.
Then, use formed positive active material among embodiment 3-1～3-9 and the comparative example 3-1～3-2, form the secondary cell shown in Fig. 1 and 2.At this moment, mode according to embodiment 1-1～1-5, form secondary cell, different is, as cathode mix, uses the formed positive active material of 86wt%, 10wt% as the graphite of electric conductor and the 4wt% mixture as the polyvinylidene fluoride (PVdF) of binding agent, as negative electrode collector 22A, use the Copper Foil of thick 10 μ m,, use 1mol/dm as electrolyte
3LiPF
6Be dissolved in the formed electrolyte of mixed solvent that contains carbonic acid glycol ester and diethyl carbonate (volume mixture thing ratio is 1: 1).
According to the mode of embodiment 1-1～1-5, formed secondary cell among embodiment 3-1～3-9 and comparative example 3-1 and the 3-2 is discharged and recharged, different is to change charging voltage, thereby determine the rated capacity and the cycle characteristics of secondary cell.At this moment, under the environment of 23 ℃ and 45 ℃, secondary cell is discharged and recharged.
In addition, the positive active material of embodiment 3-1～3-9 and comparative example 3-1 and 3-2 is adhered to the metal indium foil, and carry out ESCA (being used for chemico-analytic electron Spectrum (ElectronSpectroscopy for Chemical Analysis)) under the following conditions, so that the surface measurements element compares P/Al.
(condition of ESCA)
Measuring instrument: ULVAC-PHI, the x-ray photoelectron spectroscopy Quantera of Inc., the monochromatic Al-K α radiation (1486.6eV) of SXMX radiation source
X-ray beam diameter: 100 μ m
X ray output: 25W
Electronics neutrality condition: use flood gun of " automatically " pattern and argon rifle to be used for and journey energy (path energy): 112eV
Step value: 0.2eV
Scanning times: 20 times
Following measurement result is shown in table 3～6: the initial capacity and the conservation rate of surface-element ratio in the positive active material that uses among embodiment 3-1～3-9 and comparative example 3-1 and the 3-2 and covering amount, formed battery.Be limited to 4.55V (table 3), 4.40V (table 4), 4.30V (table 5), 4.20V (table 6) on the charging voltage.
Table 3
The charging voltage upper limit: 4.55[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 3-1 | 0.35 | 2.4 | 9.67 | 84 | 69 |
| Embodiment 3-2 | 0.51 | 2.4 | 9.68 | 83 | 69 |
| Embodiment 3-3 | 0.95 | 2.4 | 9.67 | 84 | 70 |
| Embodiment 3-4 | 2.03 | 2.4 | 9.67 | 83 | 70 |
| Embodiment 3-5 | 12.7 | 2.4 | 9.67 | 80 | 66 |
| Embodiment 3-6 | 0.35 | 0.17 | 9.71 | 77 | 52 |
| Embodiment 3-7 | 0.35 | 0.34 | 9.72 | 79 | 55 |
| Embodiment 3-8 | 0.35 | 5.1 | 9.41 | 86 | 71 |
| Embodiment 3-9 | 0.35 | 6.8 | 9.11 | 86 | 72 |
| Comparative example 3-1 | - | - | 9.72 | 68 | 35 |
| Comparative example 3-2 | - | 2.4 | 9.67 | 77 | 52 |
Table 4
The charging voltage upper limit: 4.40[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 3-1 | 0.35 | 2.4 | 9.00 | 90 | 80 |
| Embodiment 3-2 | 0.51 | 2.4 | 9.01 | 91 | 82 |
| Embodiment 3-3 | 0.95 | 2.4 | 9.01 | 91 | 83 |
| Embodiment 3-4 | 2.03 | 2.4 | 9.01 | 91 | 83 |
| Embodiment 3-5 | 12.7 | 2.4 | 9.01 | 90 | 76 |
| Embodiment 3-6 | 0.35 | 0.17 | 9.15 | 85 | 67 |
| Embodiment 3-7 | 0.35 | 0.34 | 9.15 | 87 | 75 |
| Embodiment 3-8 | 0.35 | 5.1 | 8.71 | 91 | 82 |
| Embodiment 3-9 | 0.35 | 6.8 | 8.45 | 91 | 83 |
| Comparative example 3-1 | - | - | 9.17 | 80 | 51 |
| Comparative example 3-2 | - | 2.4 | 9.00 | 85 | 65 |
Table 5
The charging voltage upper limit: 4.30[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 3-1 | 0.35 | 2.4 | 8.53 | 93 | 88 |
| Embodiment 3-2 | 0.51 | 2.4 | 8.53 | 94 | 90 |
| Embodiment 3-3 | 0.95 | 2.4 | 8.53 | 94 | 90 |
| Embodiment 3-4 | 2.03 | 2.4 | 8.53 | 94 | 90 |
| Embodiment 3-5 | 12.7 | 2.4 | 8.53 | 93 | 84 |
| Embodiment 3-6 | 0.35 | 0.17 | 8.70 | 91 | 78 |
| Embodiment 3-7 | 0.35 | 0.34 | 8.68 | 91 | 82 |
| Embodiment 3-8 | 0.35 | 5.1 | 8.25 | 93 | 88 |
| Embodiment 3-9 | 0.35 | 6.8 | 8.01 | 93 | 90 |
| Comparative example 3-1 | - | - | 8.71 | 88 | 70 |
| Comparative example 3-2 | - | 2.4 | 8.53 | 90 | 78 |
Table 6
The charging voltage upper limit: 4.20[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 3-1 | 0.35 | 2.4 | 8.11 | 94 | 91 |
| Embodiment 3-2 | 0.51 | 2.4 | 8.11 | 94 | 92 |
| Embodiment 3-3 | 0.95 | 2.4 | 8.10 | 94 | 92 |
| Embodiment 3-4 | 2.03 | 2.4 | 8.10 | 94 | 92 |
| Embodiment 3-5 | 12.7 | 2.4 | 8.10 | 94 | 89 |
| Embodiment 3-6 | 0.35 | 0.17 | 8.27 | 93 | 85 |
| Embodiment 3-7 | 0.35 | 0.34 | 8.25 | 93 | 87 |
| Embodiment 3-8 | 0.35 | 5.1 | 7.85 | 94 | 91 |
| Embodiment 3-9 | 0.35 | 6.8 | 7.63 | 94 | 91 |
| Comparative example 3-1 | - | - | 8.29 | 93 | 81 |
| Comparative example 3-2 | - | 2.4 | 8.09 | 94 | 87 |
Shown in table 3～6, when finding to comprise the compound of phosphorus and aluminium on the lithium composite xoide particle surface, can improve cycle characteristics.In addition, be 0.3 or when above at the atomic ratio (P/Al) of phosphorus and aluminium, can obtain better characteristic.
In addition, when the amount of the compound of phosphorus on the surface and aluminium was too small, the circulation improvement effect was little, measured when excessive when this, and initial capacity obviously reduces.Thereby, find preferably to comprise 0.2mol%～6.0mol% (comprising two-end-point) phosphorus and aluminium altogether with respect to the lithium composite xoide particle.
Embodiment 4-1～4-9, comparative example 4-1,4-2
After the mode according to embodiment 3-1～3-9 and comparative example 3-1 and 3-2 forms positive pole 33 and negative pole 34, form the secondary cell shown in Fig. 3 and 4.At first, aluminum positive wire 31 is attached to the end of positive electrode collector 33A, nickel system negative wire 32 is attached to the end of negative electrode collector 34A.Then, dielectric substrate 36 is arranged on positive pole 33 and the negative pole 34, this dielectric substrate 36 is by forming in the copolymer that electrolyte is carried on polyvinylidene fluoride and hexafluoropropylene.As electrolyte, use will be as the LiPF of the 0.8mol/kg of electrolytic salt
6Be dissolved in the formed electrolyte of mixture (60wt% ethylene carbonate ester and 40wt% propylene glycol carbonate) as nonaqueous solvents.
Then, after the positive pole 33 that is formed with dielectric substrate 36 on it and the negative pole 34 that is formed with dielectric substrate 36 on it and the dividing plate between them 35 are carried out lamination,, thereby form spiral winding electrode 30 with several circles of their screw windings.Subsequently, positive wire 31 and negative wire 32 are being led in the outside, under reduced pressure spiral winding electrode 30 is being sealed in the packing component 40 that laminated film makes, thereby forming the secondary cell of thick 3.8mm, wide 34mm and high 50mm.
Mode according to embodiment 1-1～1-5, the secondary cell that forms among embodiment 4-1～4-9 and comparative example 4-1 and the 4-2 is discharged and recharged, and different is, during discharging and recharging in constant current be 700mA, and change charging voltage, thereby the rated capacity and the cycle characteristics of definite secondary cell.At this moment, under the environment of 23 ℃ and 45 ℃, secondary cell is discharged and recharged.In addition, according to the mode of embodiment 3-1～3-9 and comparative example 3-1 and 3-2, surface measurements element ratio and covering amount.The result is shown in table 7～10.Be limited to 4.55V (table 7), 4.40V (table 8), 4.30V (table 9) and 4.20V (table 10) on the charging voltage.
Table 7
The charging voltage upper limit: 4.55[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 4-1 | 0.35 | 2.4 | 3.13 | 85 | 70 |
| Embodiment 4-2 | 0.51 | 2.4 | 3.13 | 85 | 70 |
| Embodiment 4-3 | 0.95 | 2.4 | 3.13 | 85 | 71 |
| Embodiment 4-4 | 2.03 | 2.4 | 3.12 | 86 | 71 |
| Embodiment 4-5 | 12.7 | 2.4 | 3.13 | 82 | 68 |
| Embodiment 4-6 | 0.35 | 0.17 | 3.17 | 79 | 58 |
| Embodiment 4-7 | 0.35 | 0.34 | 3.16 | 80 | 66 |
| Embodiment 4-8 | 0.35 | 5.1 | 3.05 | 88 | 72 |
| Embodiment 4-9 | 0.35 | 6.8 | 3.00 | 88 | 73 |
| Comparative example 4-1 | - | - | 3.19 | 69 | 40 |
| Comparative example 4-2 | - | 2.4 | 3.12 | 79 | 57 |
Table 8
The charging voltage upper limit: 4.40[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 4-1 | 0.35 | 2.4 | 2.91 | 91 | 82 |
| Embodiment 4-2 | 0.51 | 2.4 | 2.91 | 92 | 83 |
| Embodiment 4-3 | 0.95 | 2.4 | 2.91 | 92 | 83 |
| Embodiment 4-4 | 2.03 | 2.4 | 2.91 | 92 | 84 |
| Embodiment 4-5 | 12.7 | 2.4 | 2.91 | 91 | 78 |
| Embodiment 4-6 | 0.35 | 0.17 | 2.96 | 86 | 69 |
| Embodiment 4-7 | 0.35 | 0.34 | 2.95 | 88 | 76 |
| Embodiment 4-8 | 0.35 | 5.1 | 2.83 | 92 | 84 |
| Embodiment 4-9 | 0.35 | 6.8 | 2.77 | 93 | 85 |
| Comparative example 4-1 | - | - | 2.96 | 82 | 55 |
| Comparative example 4-2 | - | 2.4 | 2.91 | 86 | 66 |
Table 9
The charging voltage upper limit: 4.30[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 4-1 | 0.35 | 2.4 | 2.75 | 94 | 89 |
| Embodiment 4-2 | 0.51 | 2.4 | 2.75 | 94 | 90 |
| Embodiment 4-3 | 0.95 | 2.4 | 2.74 | 94 | 90 |
| Embodiment 4-4 | 2.03 | 2.4 | 2.74 | 94 | 90 |
| Embodiment 4-5 | 12.7 | 2.4 | 2.76 | 94 | 85 |
| Embodiment 4-6 | 0.35 | 0.17 | 2.81 | 92 | 80 |
| Embodiment 4-7 | 0.35 | 0.34 | 2.81 | 92 | 83 |
| Embodiment 4-8 | 0.35 | 5.1 | 2.69 | 94 | 90 |
| Embodiment 4-9 | 0.35 | 6.8 | 2.62 | 94 | 92 |
| Comparative example 4-1 | - | - | 2.81 | 89 | 72 |
| Comparative example 4-2 | - | 2.4 | 2.75 | 91 | 80 |
Table 10
The charging voltage upper limit: 4.20[V]
| Surface P/Al ratio | Covering amount [mol%] | Initial capacity (23 ℃) [Wh] | Conservation rate (23 ℃) [%] | Conservation rate (45 ℃) [%] | |
| Embodiment 4-1 | 0.35 | 2.4 | 2.62 | 95 | 92 |
| Embodiment 4-2 | 0.51 | 2.4 | 2.62 | 95 | 92 |
| Embodiment 4-3 | 0.95 | 2.4 | 2.62 | 95 | 92 |
| Embodiment 4-4 | 2.03 | 2.4 | 2.61 | 95 | 92 |
| Embodiment 4-5 | 12.7 | 2.4 | 2.62 | 95 | 90 |
| Embodiment 4-6 | 0.35 | 0.17 | 2.66 | 94 | 87 |
| Embodiment 4-7 | 0.35 | 0.34 | 2.65 | 95 | 89 |
| Embodiment 4-8 | 0.35 | 5.1 | 2.57 | 95 | 93 |
| Embodiment 4-9 | 0.35 | 6.8 | 2.48 | 95 | 93 |
| Comparative example 4-1 | - | - | 2.66 | 94 | 83 |
| Comparative example 4-2 | - | 2.4 | 2.62 | 95 | 89 |
Shown in table 7～10, find when comprising the compound of phosphorus and aluminium on the lithium composite xoide particle surface, can improve cycle characteristics.In addition, when the atomic ratio (P/Al) of phosphorus on the surface and aluminium is 0.3 or when above, can obtain better characteristic.
In addition, when the amount of the compound of phosphorus on the surface and aluminium was too small, circulation improvement effect was little, measured when excessive when this, and initial capacity obviously reduces.Thereby, with respect to the lithium composite xoide particle, preferably comprise 0.2mol～6.0mol% (comprising two-end-point) phosphorus and aluminium altogether.
Embodiment 5-1～5-5, comparative example 5-1～5-3
Form positive active material by following steps.In embodiment 5-1, at first, mix three hypophosphite monohydrate manganese (Mn
3(PO
4)
23H
2O) and lithium phosphate (Li
3PO
4), and grind in the pure water as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.3 μ m).In this slurry, add average group and become Li
1.03Co
0.98Al
0.01Mg
0.01O
2And record the lithium composite xoide particle that average grain diameter is 13 μ m by laser scattering method, and stir, thereby form solidliquid mixture, in 200 ℃ of these solidliquid mixtures of drying, and in 800 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is 2.0mol%.
In embodiment 5-2, form positive active material according to the mode of embodiment 5-1, different is that with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is respectively 3.0mol% and 2.0mol%.
In embodiment 5-3, form positive active material according to the mode of embodiment 5-1, different is that with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is respectively 2.0mol% and 3.0mol%.
In embodiment 5-4, form positive active material according to the mode of embodiment 5-1, different is to mix three hypophosphite monohydrate manganese and lithium carbonate (Li
2CO
3), and with respect to the lithium composite xoide powder, the covering amount of manganese, phosphorus and lithium is respectively 3.0mol%, 2.0mol% and 3.0mol%.
In embodiment 5-5, form positive active material according to the mode of embodiment 5-1, different is use three hypophosphite monohydrate manganese, and do not use lithium phosphate, thereby with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus to be respectively 3.0mol% and 2.0mol%.
According to the mode of embodiment 1-1～1-5, the surface-element of measuring the formed positive active material of embodiment 5-1 is formed and is distributed along the element of positive active material depth direction.The result as shown in Figure 9.Thereby, find that the content of phosphorus and manganese reduces to inside from the surface, and the content of cobalt increases.
Then,, use the formed positive active material of embodiment 5-1～5-5, form secondary cell according to the mode of embodiment 3-1～3-9.
In addition, as the comparative example 5-1 with respect to embodiment 5-1～5-5, form secondary cell according to the mode of embodiment 5-1～5-5, different is, is blended in lithium composite xoide particle (Li in the water by use
1.03Co
0.98Al
0.01Mg
0.01O
2), form positive active material.
In addition, 5-2 and 5-3 as a comparative example form secondary cell according to the mode of embodiment 5-1～5-5, and different is to use lithium composite xoide particle (Li used among embodiment 5-1～5-5
1.03Co
0.98Al
0.01Mg
0.01O
2) and diammonium hydrogen phosphate ((NH
4)
2HPO
3) be dissolved in the mixture of the solution that pure water forms as positive active material.At this moment, with respect to the lithium composite xoide powder, the covering amount of phosphorus is 1.0mol% in comparative example 5-2, is 3.0mol% in comparative example 5-3.
The initial capacity, high temperature of determining embodiment 5-1～5-5 and the formed secondary cell of comparative example 5-1～5-3 by following steps be capability retention and the low temperature capability retention during circulation 200 times down.
＜initial capacity 〉
Be under 23 ℃ the condition in ambient temperature, after under constant current and constant voltage, secondary cell being charged, charging current is 1000mA, charging voltage is 4.4V, and the charging interval is 3 hours, is under 23 ℃ the condition in ambient temperature, under constant current, secondary cell is discharged, discharging current is 800mA, and final voltage (end voltage) is 3.0V, thereby measures the initial capacity of secondary cell.The result is as shown in table 11.
＜high temperature is the capability retention during circulation 200 times down 〉
In ambient temperature is that 45 ℃, charging current are that 1000mA, charging voltage are 4.4V, charging interval to be under 3 hours the condition, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that 45 ℃, discharging current are that 800mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thus the initial capacity of measurement secondary cell.Then, under the condition identical, repeat charge and discharge cycles, the discharge capacity when measuring circulation 200 times then with the condition of measuring initial capacity.When determining circulation 200 times then with respect to the capability retention of secondary cell initial capacity.The result is as shown in table 11.
＜low temperature capability retention 〉
In ambient temperature is that 23 ℃, charging current are that 1000mA, charging voltage are 4.4V, charging interval to be under 3 hours the condition, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that-20 ℃～23 ℃, discharging current are that 2400mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, measure the discharge capacity of secondary cell at each temperature then.When then, determining that ambient temperature is 0 ℃ ,-10 ℃ and-20 ℃ with respect to the discharge capacitance of 23 ℃ of following discharge capacities of secondary cell.The result is as shown in table 11.
In addition, by the step identical with above-mentioned steps, the initial capacity, high temperature of determining the secondary cell of embodiment 5-1 and comparative example 5-1 be capability retention and the low temperature capability retention during circulation 200 times down, and different is that charging voltage becomes 4.20V, 4.30V, 4.40V, 4.50V and 4.60V.The result is as shown in table 12.
Table 11
Lithium composite xoide: Li
1.03Co
0.98Al
0.01Mg
0.01O
2
The charging voltage upper limit: 4.40[V]
| Coat element [mol%] | Initial capacity (23 ℃) [Wh] | High temperature capability retention [%] (45 ℃) | Low temperature capability retention [%] | |||||
| | P | Li | 0℃ | -10℃ | -20℃ | |||
| Embodiment 5-1 | 2.0 | 2.0 | 2.0 | 9.62 | 72.8 | 88.5 | 81.4 | 66.2 |
| Embodiment 5-2 | 3.0 | 2.0 | 2.0 | 9.54 | 71.7 | 87.6 | 78.5 | 63.8 |
| Embodiment 5-3 | 2.0 | 3.0 | 3.0 | 9.51 | 73.4 | 89.4 | 81.9 | 66.3 |
| Embodiment 5-4 | 3.0 | 2.0 | 3.0 | 9.56 | 75.2 | 89.2 | 82.0 | 67.1 |
| Embodiment 5-5 | 3.0 | 2.0 | - | 9.58 | 70.1 | 87.2 | 81.1 | 66.8 |
| Comparative example 5-1 | - | - | - | 9.89 | 51.4 | 83.7 | 71.9 | 55.9 |
| Comparative example 5-2 | - | 1.0 | - | 9.53 | 57.8 | 79.2 | 70.4 | 54.1 |
| Comparative example 5-3 | - | 3.0 | - | 9.29 | 64.0 | 81.7 | 70.1 | 54.8 |
Table 12
| Lithium composite xoide | Coat element [mol%] | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | High temperature capability retention [%] (45 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20℃ | |||||
| Embodiment 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 2.0 | 2.0 | 4.60 | 10.52 | 65.8 | 89.5 | 83.8 | 67.0 |
| Comparative example 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | 4.60 | 10.86 | 31.4 | 83.1 | 72.9 | 54.9 |
| Embodiment 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 2.0 | 2.0 | 4.50 | 10.22 | 67.7 | 89.7 | 84.4 | 67.3 |
| Comparative example 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | 4.50 | 10.75 | 38.1 | 83.1 | 72.9 | 54.9 |
| Embodiment 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 2.0 | 2.0 | 4.40 | 9.62 | 72.8 | 88.5 | 81.4 | 66.2 |
| Comparative example 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | 4.40 | 9.89 | 45.1 | 83.7 | 71.9 | 55.9 |
| Embodiment 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 2.0 | 2.0 | 4.30 | 9.35 | 74.2 | 89.9 | 84.0 | 66.8 |
| Comparative example 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | 4.30 | 9.65 | 47.4 | 83.2 | 71.8 | 55.2 |
| Embodiment 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 2.0 | 2.0 | 4.20 | 9.11 | 75.5 | 89.3 | 83.1 | 66.5 |
| Comparative example 5-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | 4.20 | 9.51 | 55.8 | 81.6 | 71.5 | 55.5 |
By the result in the table 11 obviously as can be known, under the situation of the compound of the compound that comprises phosphorous and manganese on the lithium composite xoide particle surface or phosphorous, manganese and lithium, compare with the situation that does not comprise these compounds on the lithium composite xoide particle surface, the initial capacity of secondary cell reduces slightly, but high temperature down capability retention and the low temperature capability retention during circulation 200 times improve.At this moment, even find to change within the specific limits the ratio of phosphorus and manganese, the capability retention 200 times time the and the effect of low temperature capability retention of circulating high temperature under still can be improved.In addition, find only to comprise on the particle surface under the situation of phosphorus, high temperature is the capability retention deficiency during circulation 200 times down, and the effect of the low temperature capability retention that is not improved.
By the result in the table 12 obviously as can be known, under the situation of the compound that comprises phosphorous and manganese on the lithium composite xoide particle surface, compare with the situation that does not comprise this compound on the particle surface, under the condition of the charging voltage upper limit in 4.2～4.6V scope, the initial capacity of secondary cell has reduction slightly, but improved high temperature capability retention and the low temperature capability retention during circulation 200 times down.
Embodiment 6-1～6-5
Mode according to embodiment 3-1～3-9 forms secondary cell, and different is to use by changing the formed positive active material of combined amount of three hypophosphite monohydrate manganese and lithium phosphate.At this moment, manganese and phosphorus equate with respect to the covering amount of lithium composite xoide powder, and are 5.7mol% (embodiment 6-1), 3.0mol% (embodiment 6-2), 1.5mol% (embodiment 6-3), 0.3mol% (embodiment 6-4) and 0.15mol% (embodiment 6-5).
According to the mode of embodiment 5-1～5-5, the initial capacity, high temperature of measuring the formed secondary cell of embodiment 6-1～6-5 be capability retention and the low temperature capability retention during circulation 200 times down.Charging voltage is 4.4V.The result is as shown in table 13.
Table 13
| Lithium composite xoide | Coat element [mol%] | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | High temperature capability retention [%] (45 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20℃ | |||||
| Embodiment 6-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 5.7 | 5.7 | 4.40 | 8.63 | 66.3 | 85.3 | 74.8 | 58.1 |
| Embodiment 6-2 | 3.0 | 3.0 | 9.27 | 70.5 | 87.3 | 80.2 | 65.0 | ||
| Embodiment 5-1 | 2.0 | 2.0 | 9.62 | 72.8 | 88.5 | 81.4 | 66.2 | ||
| Embodiment 6-3 | 1.5 | 1.5 | 9.71 | 73.4 | 89.4 | 81.9 | 66.7 | ||
| Embodiment 6-4 | 0.3 | 0.3 | 9.82 | 66.5 | 86.7 | 79.8 | 65.3 | ||
| Embodiment 6-5 | 0.15 | 0.15 | 9.85 | 65.2 | 84.8 | 74.2 | 57.3 | ||
According to the result in the table 13 obviously as can be known, when adding to phosphorus and manganese in the lithium composite xoide powder and heating, high temperature capability retention and the low temperature capability retention during circulation 200 times down improves.In addition, with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is preferably in 0.1mol%～6.0mol% scope (comprising two-end-point).This be because, when covering amount was too small, the capability retention 200 times time the and the effect of low temperature capability retention of circulating that fully be not improved high temperature under measured when excessive when this, the initial capacity of secondary cell reduces greatly.
Embodiment 7, comparative example 7
Form positive active material by following steps.At first, mix three hypophosphite monohydrate manganese (Mn
3(PO
4)
23H
2O) and lithium phosphate (Li
3PO
4), and grind in the pure water as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.4 μ m).In this slurry, add average group and become Li
1.02Ni
0.5Co
0.2Mn
0.3O
2And record lithium composite xoide particle and the stirring that average grain diameter is 12 μ m by laser scattering method, thereby the formation solidliquid mixture carries out drying in 200 ℃ to this solidliquid mixture, and in 900 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is 2.0mol%.Subsequently, according to the mode of embodiment 3-1～3-9, form secondary cell.
In addition, as the comparative example 7 with respect to embodiment 7, form secondary cell according to the mode of embodiment 7, different is the lithium composite xoide particle (Li that uses in embodiment 7
1.02Ni
0.5Co
0.2Mn
0.3O
2) in water, stir after, carry out drying in 200 ℃, and in 800 ℃ of heating 5 hours, slowly cooling then, thereby form positive active material.
According to the mode of embodiment 5-1 and comparative example 5-1, the initial capacity, high temperature of determining embodiment 7 and comparative example 7 formed secondary cells be capability retention and the low temperature capability retention during circulation 200 times down.The result is as shown in table 14.
Table 14
| Lithium composite xoide | Coat element [mol%] | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | High temperature capability retention [%] (45 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20℃ | |||||
| Embodiment 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.0 | 2.0 | 4.60 | 9.42 | 72.8 | 85.3 | 80.1 | 65.1 |
| Comparative example 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | 4.60 | 9.82 | 37.3 | 78.2 | 71.1 | 52.7 |
| Embodiment 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.0 | 2.0 | 4.50 | 9.15 | 75.9 | 85.1 | 80.7 | 64.1 |
| Comparative example 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | 4.50 | 9.54 | 39.1 | 77.5 | 70.8 | 51.4 |
| Embodiment 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.0 | 2.0 | 4.40 | 8.58 | 81.8 | 86.4 | 81.1 | 64.6 |
| Comparative example 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | 4.40 | 8.94 | 48.1 | 82.1 | 70.3 | 50.8 |
| Embodiment 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.0 | 2.0 | 4.30 | 8.27 | 84.2 | 85.2 | 79.8 | 61.7 |
| Comparative example 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | 4.30 | 8.72 | 56.4 | 80.5 | 69.5 | 51.4 |
| Embodiment 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.0 | 2.0 | 4.20 | 8.15 | 85.5 | 84.8 | 78.0 | 63.6 |
| Comparative example 7 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | 4.20 | 8.50 | 79.3 | 76.1 | 68.3 | 50.7 |
According to the result in the table 14 obviously as can be known, on average form in use by Li
1.0Ni
0.5Co
0.2Mn
0.3O
2The lithium composite xoide of expression is as the lithium composite xoide that is used for core, and under the situation of the compound that comprises phosphorous, manganese and lithium on the lithium composite xoide particle surface, compare with the situation that does not comprise this compound, in the charging voltage upper limit in 4.2V～4.6V scope under the condition of (comprising two-end-point), the initial capacity of secondary cell has decline slightly, but high temperature down capability retention and the low temperature capability retention during circulation 200 times improve.
Embodiment 8, comparative example 8
Form positive active material by following steps.At first, mix three hypophosphite monohydrate manganese and lithium phosphates, and in pure water, grind, thereby form slurry (containing the solid portion that average grain diameter is 0.4 μ m) as decentralized medium by ball-milling method.In this slurry, add average group and become Li
1.05Mn
1.85Al
0.1O
4And record the lithium composite xoide particle that average grain diameter is 15 μ m with spinel structure by laser scattering method, and stir, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 800 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to the lithium composite xoide powder, the covering amount of manganese and phosphorus is 2.0mol%.Subsequently, the mode according to embodiment 3-1～3-9 forms secondary cell.
In addition, as the comparative example 8 with respect to embodiment 8, form secondary cell according to the mode of embodiment 3-1～3-9, different is the lithium composite xoide particle (Li that uses in embodiment 8
1.05Mn
1.85Al
0.1O
4) put into water and stir after, carry out drying and in 800 ℃ of heating 5 hours in 200 ℃, slowly cooling then, thereby form positive active material.
Measure the initial capacity and the low temperature capability retention of embodiment 8 and comparative example 8 formed secondary cells by following steps.
＜initial capacity 〉
In ambient temperature is that 23 ℃, charging voltage are that 4.2V, charging current are 800mA, charging interval to be under 2.5 hours the condition, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that 23 ℃, discharging current are that 500mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thus the initial capacity of measurement secondary cell.The result is as shown in Table 15.
＜low temperature capability retention 〉
Be under 23 ℃ the condition in ambient temperature, after under constant current and constant voltage, secondary cell being charged, charging voltage is 4.2V, charging current is 800mA, and the charging interval is 2.5 hours, is under-20 ℃～23 ℃ the condition in ambient temperature, under constant current, secondary cell is discharged, discharging current is 500mA, and final voltage is 3.0V, thereby measures the discharge capacity of secondary cell at each temperature.Then, the secondary cell discharge capacity when being 23 ℃ with respect to ambient temperature is determined the capability retention when ambient temperature is 0 ℃ ,-10 ℃ and-20 ℃.The result is as shown in Table 15.
Table 15
| Lithium composite xoide | Coat element [mol%] | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20℃ | ||||
| Embodiment 8 | Li 1.05Mn 1.85Al 0.1O 4 | 2.0 | 2.0 | 4.20 | 6.27 | 87.1 | 72.6 | 32.9 |
| Comparative example 8 | Li 1.05Mn 1.85Al 0.1O 4 | - | - | 4.20 | 6.45 | 80.5 | 57.5 | 24.4 |
According to the result in the table 15 obviously as can be known, the lithium composite xoide that has spinel structure in use is as the lithium composite xoide that is used for core, and when on the lithium composite xoide surface, comprising the compound of phosphorous, manganese and lithium, compare with the situation that does not comprise this compound on the surface, initial capacity has decline slightly, but the low temperature capability retention improves.
Embodiment 9-1～9-6, comparative example 9-1,9-2
Form positive active material by following steps.In embodiment 9-1, mix 55.16g eight hypophosphite monohydrate magnesium ((Mg
3PO
4) 8H
2O) and 15.99g lithium phosphate (Li
3PO
4), and grind in the pure water as decentralized medium by ball-milling method, thereby form slurry (containing the solid portion that average grain diameter is 0.4 μ m).Then, in this slurry, add 1kg and record the lithium composite xoide particle that average grain diameter is 13 μ m by laser scattering method, and stir, thereby the formation solidliquid mixture carries out drying in 200 ℃ to this solidliquid mixture, and in 800 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to lithium composite xoide, the covering amount of magnesium and phosphorus is 3.8mol%.
In embodiment 9-2, form positive active material according to the mode of embodiment 9-1, different is mix 44.83g eight hypophosphite monohydrate magnesium and 13.00g lithium phosphate, and with respect to lithium composite xoide, the covering amount of magnesium and phosphorus to be 3.1mol%.
In embodiment 9-3, form positive active material according to the mode of embodiment 9-1, different is mix 33.28g eight hypophosphite monohydrate magnesium and 9.65g lithium phosphate, and with respect to lithium composite xoide, the covering amount of magnesium and phosphorus to be 2.3mol%.
In embodiment 9-4, form secondary cell according to the mode of embodiment 9-1, different is mix 10.87g eight hypophosphite monohydrate magnesium and 3.15g lithium phosphate, and with respect to lithium composite xoide, the covering amount of magnesium and phosphorus to be 0.8mol%.
In embodiment 9-5, form positive active material according to the mode of embodiment 9-1, different is mix 5.41g eight hypophosphite monohydrate magnesium and 1.57g lithium phosphate, and with respect to lithium composite xoide, the covering amount of magnesium and phosphorus to be 0.4mol%.
In embodiment 9-6, form positive active material according to the mode of embodiment 9-1, different is mix 6.37g eight hypophosphite monohydrate magnesium and 21.96g lithium phosphate, and with respect to lithium composite xoide, the covering amount of magnesium and phosphorus to be 0.15mol%.
The surface-element of measuring the formed positive active material of embodiment 9-3 according to the mode of embodiment 1-1～1-5 is formed and is distributed along the element of positive active material depth direction.The result as shown in figure 10.Thereby the content of finding phosphorus and manganese reduces to inside from the surface, and the content of cobalt increases.
Then, according to the mode of embodiment 3-1～3-9, use formed positive active material formation secondary cell among embodiment 9-1～9-6.
As comparative example 9-1 with respect to embodiment 9-1～9-6, form secondary cell according to the mode of embodiment 9-1～9-6, different is the lithium composite xoide (Li that uses in embodiment 9-1～9-3
1.03Co
0.98Al
0.01Mg
0.01O
2) put into water and stir after, in 200 ℃ this lithium composite xoide is carried out drying, and in 800 ℃ of heating 5 hours, thereby forms positive active material.
In addition, as comparative example 9-2 with respect to embodiment 9-1～9-6, form secondary cell according to the mode of embodiment 9-1～9-6, different is, be dissolved in pure water at the 41.9g diammonium hydrogen phosphate and form in the solution, add the lithium composite xoide (Li that uses among 1kg embodiment 9-1～9-6
1.03Co
0.98Al
0.01Mg
0.01O
2) and stir, in 200 ℃ this lithium composite xoide is carried out drying, and in 800 ℃ of heating 5 hours, thereby positive active material formed.At this moment, with respect to the lithium composite xoide powder, the covering amount of phosphorus is 3.0mol%.
Measure the initial capacity and the low temperature capability retention of embodiment 9-1～9-6 and comparative example 9-1 and the formed secondary cell of 9-2 by following steps.
＜initial capacity 〉
In ambient temperature is that 23 ℃, charging current are to be limited on 1000mA, the charging voltage under the condition of 4.2V～4.6V, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that 23 ℃, discharging current are that 2400mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thus the discharge capacity of measurement secondary cell.The result is shown in table 16.
＜low temperature capability retention 〉
In ambient temperature is that 23 ℃, charging current are to be limited on 1000mA, the charging voltage under the condition of 4.2V～4.6V, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that-20 ℃～23 ℃, discharging current are that 2400mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thereby measure the discharge capacity of secondary cell at each temperature.Capability retention when then, the secondary cell discharge capacity when being 23 ℃ with respect to ambient temperature, measures ambient temperature are 0 ℃ ,-10 ℃ and-20 ℃.The result is shown in table 16.
Table 16
| Lithium composite xoide | Coat element [mol%] | Surface P/Mg ratio | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | Low temperature capability retention [%] | ||||
| Mg | P | 0℃ | -10℃ | -20℃ | |||||
| Embodiment 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 3.8 | 3.8 | 0.60 | 4.60 | 10.03 | 83.5 | 73.6 | 57.1 |
| Embodiment 9-2 | 3.1 | 3.1 | 0.58 | 10.28 | 88.3 | 83.4 | 66.2 | ||
| Embodiment 9-3 | 2.3 | 2.3 | 0.57 | 10.52 | 89.5 | 83.8 | 67.0 | ||
| Embodiment 9-4 | 0.8 | 0.8 | 0.55 | 10.78 | 88.0 | 80.4 | 66.3 | ||
| Embodiment 9-5 | 0.4 | 0.4 | 0.54 | 10.80 | 87.7 | 78.8 | 62.3 | ||
| Embodiment 9-6 | 0.15 | 0.15 | 0.48 | 10.82 | 84.5 | 73.7 | 58.1 | ||
| Comparative example 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | - | 4.60 | 10.86 | 83.1 | 72.9 | 54.9 |
| Comparative example 9-2 | - | 3.0 | - | 10.27 | 80.8 | 69.1 | 53.4 | ||
| Embodiment 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 3.8 | 3.8 | 0.60 | 4.50 | 9.71 | 83.7 | 73.7 | 57.1 |
| Embodiment 9-2 | 3.1 | 3.1 | 0.58 | 10.07 | 88.6 | 83.7 | 67.0 | ||
| Embodiment 9-3 | 2.3 | 2.3 | 0.57 | 10.22 | 89.7 | 84.4 | 67.3 | ||
| Embodiment 9-4 | 0.8 | 0.8 | 0.55 | 10.48 | 88.9 | 80.8 | 66.8 | ||
| Embodiment 9-5 | 0.4 | 0.4 | 0.54 | 10.58 | 88.4 | 78.8 | 62.3 | ||
| Embodiment 9-6 | 0.15 | 0.15 | 0.48 | 10.70 | 84.7 | 73.9 | 58.4 | ||
| Comparative example 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | - | 4.50 | 10.75 | 83.1 | 72.9 | 54.9 |
| Comparative example 9-2 | - | 3.0 | - | 9.98 | 81.6 | 68.9 | 52.9 | ||
| Embodiment 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 3.8 | 3.8 | 0.60 | 4.40 | 8.94 | 83.9 | 74.0 | 58.8 |
| Embodiment 9-2 embodiment 9-3 | 3.1 2.3 | 3.1 2.3 | 0.58 0.57 | 9.34 9.58 | 89.5 89.9 | 83.4 83.7 | 66.2 66.8 | ||
| Embodiment 9-4 | 0.8 | 0.8 | 0.55 | 9.82 | 88.6 | 78.8 | 65.9 | ||
| Embodiment 9-5 | 0.4 | 0.4 | 0.54 | 9.84 | 88.1 | 78.1 | 64.3 | ||
| Embodiment 9-6 | 0.15 | 0.15 | 0.48 | 9.86 | 84.7 | 73.9 | 58.2 | ||
| Comparative example 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | - | 4.40 | 9.89 | 83.7 | 71.9 | 55.9 |
| Comparative example 9-2 | - | 3.0 | - | 9.29 | 81.7 | 70.1 | 54.8 | ||
| Embodiment 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 3.8 | 3.8 | 0.60 | 4.30 4.30 | 8.70 | 83.5 | 73.9 | 57.4 |
| Embodiment 9-2 | 3.1 | 3.1 | 0.58 | 9.21 | 89.7 | 83.4 | 65.8 | ||
| Embodiment 9-3 | 2.3 | 2.3 | 0.57 | 9.35 | 89.9 | 84.0 | 66.8 | ||
| Embodiment 9-4 | 0.8 | 0.8 | 0.55 | 9.59 | 88.3 | 83.4 | 65.3 | ||
| Embodiment 9-5 | 0.4 | 0.4 | 0.54 | 9.60 | 87.7 | 82.3 | 64.8 | ||
| Embodiment 9-6 comparative example 9-1 | 0.15 - | 0.15 - | 0.48 - | 9.62 9.65 | 84.8 83.2 | 73.7 71.8 | 58.1 55.2 | ||
| Comparative example 9-2 | - | 3.0 | - | 9.20 | 81.6 | 70.2 | 52.9 | ||
| Embodiment 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | 3.8 | 3.8 | 0.60 | 4.20 | 8.82 | 82.1 | 73.6 | 57.0 |
| Embodiment 9-2 | 3.1 | 3.1 | 0.58 | 9.05 | 88.7 | 82.7 | 66.1 | ||
| Embodiment 9-3 | 2.3 | 2.3 | 0.57 | 9.11 | 89.3 | 83.1 | 66.5 | ||
| Embodiment 9-4 | 0.8 | 0.8 | 0.55 | 9.19 | 88.5 | 82.1 | 65.9 | ||
| Embodiment 9-5 | 0.4 | 0.4 | 0.54 | 9.45 | 88.0 | 80.8 | 64.8 | ||
| Embodiment 9-6 | 0.15 | 0.15 | 0.48 | 9.47 | 82.5 | 73.6 | 57.1 | ||
| Comparative example 9-1 | Li 1.03Co 0.98Al 0.01Mg 0.01O 2 | - | - | - | 4.20 | 9.51 | 81.6 | 71.5 | 55.5 |
| Comparative example 9-2 | - | 3.0 | - | 9.02 | 79.0 | 69.5 | 53.0 | ||
According to the result in the table 16 obviously as can be known, under the situation of phosphorous and compound magnesium being added in the lithium composite xoide powder, compare with the situation of not adding compound, initial capacity has decline slightly, but the low temperature capability retention improves.In addition, the covering amount of phosphorus and magnesium preferably (comprises two-end-point) in the scope of 0.1mol%～4.0mol%.This be because, measure when too small when this, the low temperature capability retention reduces, and measures when excessive when this, initial capacity obviously descends.
Form positive active material by following steps.At first, mix 33.28g eight hypophosphite monohydrate magnesium and 9.65g lithium phosphate, thereby form slurry (containing the solid portion that average grain diameter is 0.4 μ m).In this slurry, add average group and become Li
1.02Ni
0.5Co
0.2Mn
0.3O
2And record the lithium composite xoide particle that average grain diameter is 12 μ m by laser scattering method, and stir, thereby form solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 900 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to lithium composite xoide, the covering amount of magnesium and phosphorus is 2.3mol%.Subsequently, the mode according to embodiment 3-1～3-9 obtains secondary cell.
In addition, as the comparative example 10 with respect to embodiment 10, form secondary cell according to the mode of embodiment 10, different is the lithium composite xoide Li that uses in embodiment 10
1.02Ni
0.5Co
0.2Mn
0.3O
2After putting into water and stirring, this lithium composite xoide is carried out drying in 200 ℃, and in 900 ℃ of heating 5 hours, thereby positive active material formed.
According to the mode of embodiment 9-1, determine the initial capacity and the low temperature capability retention of embodiment 10 and comparative example 10 formed secondary cells.The result is shown in table 17.
Table 17
| Lithium composite xoide | Coat element [mol%] | Surface P/Mg ratio | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20 | |||||
| Embodiment | |||||||||
| 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.3 | 2.3 | 0.55 | 4.60 | 9.42 | 88.3 | 80.0 | 64.6 |
| Comparative example 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | - | 4.60 | 9.82 | 82.2 | 71.3 | 52.7 |
| |
Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.3 | 2.3 | 0.55 | 4.50 | 9.15 | 87.6 | 79.8 | 63.1 |
| Comparative example 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | - | 4.50 | 9.54 | 80.5 | 57.5 | 51.4 |
| |
Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.3 | 2.3 | 0.55 | 4.40 | 8.58 | 87.4 | 80.0 | 63.6 |
| Comparative example 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | - | 4.40 | 8.94 | 82.1 | 71.3 | 50.8 |
| |
Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.3 | 2.3 | 0.55 | 4.30 | 8.27 | 86.2 | 72.8 | 61.7 |
| Comparative example 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | - | 4.30 | 8.72 | 80.5 | 62.5 | 51.4 |
| |
Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | 2.3 | 2.3 | 0.55 | 4.20 | 8.15 | 87.4 | 80.0 | 64.6 |
| Comparative example 10 | Li 1.02Ni 0.5Co 0.2Mn 0.3O 2 | - | - | - | 4.20 | 8.50 | 81.1 | 70.3 | 50.7 |
According to the result in the table 17 obviously as can be known, using Li
1.02Ni
0.5Co
0.2Mn
0.3O
2As the lithium composite xoide that is used for core, and comprise on the surface under the situation of compound of phosphorous, magnesium and lithium, compare with the situation that does not comprise this compound on the surface, the initial capacity of battery has decline slightly, but the low temperature capability retention improves.
Form positive active material by following steps.At first, mix 27.59g eight hypophosphite monohydrate magnesium and 8.00g lithium phosphate, and in pure water, grind, thereby form slurry (average grain diameter is the solid portion of 0.4 μ n) as decentralized medium by ball-milling method.In this slurry, add average group and become Li
1.05Mn
1.85Al
0.1O
4And record the lithium composite xoide particle that average grain diameter is 14 μ m with spinel structure by laser scattering method, and stir, thereby formation solidliquid mixture, in 200 ℃ this solidliquid mixture is carried out drying, and in 800 ℃ of heating 5 hours, slowly cooling then, thus positive active material formed.At this moment, with respect to lithium composite xoide, the covering amount of magnesium and phosphorus is 3.4mol%.Subsequently, according to the mode of embodiment 3-1～3-9, form secondary cell.
In addition, as the comparative example 11 with respect to embodiment 11, form secondary cell according to the mode of embodiment 11, different is to be used for the lithium composite xoide Li of core in embodiment 11
1.05Mn
1.85Al
0.1O
4After putting into water and stirring, this lithium composite xoide is carried out drying in 200 ℃, and in 900 ℃ of heating 5 hours, thereby positive active material formed.
Determine the initial capacity and the low temperature capability retention of embodiment 11 and comparative example 11 formed secondary cells by following steps.
＜initial capacity 〉
In ambient temperature is that 23 ℃, charging voltage are that 4.2V, charging current are 800mA, charging interval to be under 2.5 hours the condition, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that 23 ℃, discharging current are that 500mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thus the initial capacity of measurement secondary cell.The result is shown in table 18.
＜low temperature capability retention 〉
In ambient temperature is that 23 ℃, charging voltage are that 4.2V, charging current are 800mA, charging interval to be under 2.5 hours the condition, after under constant current and constant voltage, secondary cell being charged, in ambient temperature is that-20 ℃～23 ℃, discharging current are that 500mA, final voltage are under the condition of 3.0V, under constant current, secondary cell is discharged, thereby measure the discharge capacity of secondary cell at each temperature.Then, the secondary cell discharge capacity when being 23 ℃ with respect to ambient temperature is determined the capability retention when ambient temperature is 0 ℃ ,-10 ℃ and-20 ℃.The result is shown in table 18.
Table 18
| Lithium composite xoide | Coat element [mol%] | Surface P/Mg ratio | The charging voltage upper limit [V] | Initial capacity (23 ℃) [Wh] | Low temperature capability retention [%] | ||||
| | P | 0℃ | -10℃ | -20 | |||||
| Embodiment | |||||||||
| 11 | Li 1.05Mn 1.85Al 0.1O 4 | 3.4 | 3.4 | 0.53 | 4.20 | 6.46 | 89.4 | 80.0 | 64.6 |
| Comparative example 11 | Li 1.05Mn 1.85Al 0.1O 4 | - | - | - | 4.20 | 6.65 | 81.1 | 70.3 | 50.7 |
According to the result in the table 18 obviously as can be known, the Li that has spinel structure in use
1.05Mn
1.85Al
0.1O
4As the lithium composite xoide that is used for core, and comprise on the surface under the situation of compound of phosphorous, magnesium and lithium, compare with the situation that does not comprise this compound on the particle surface, initial capacity has decline slightly, but the low temperature capability retention improves.
Although invention has been described for reference implementation scheme and embodiment, the invention is not restricted to above-mentioned embodiment and embodiment, and can carry out various changes.For example, in above-mentioned embodiment or embodiment, described and used as the electrolyte of liquid electrolyte or the gel electrolyte of polymer compound carrying electrolyte; Yet, can use any other electrolyte.Other electrolytical example comprises: polymer dielectric, and wherein electrolytic salt is dispersed in the polymer compound with ionic conductivity; The inorganic solid electrolyte that the ionic conductivity pottery forms; Ionic conductivity glass or ionic crystals; Molten salt electrolyte; With their mixture.
In addition, in above-mentioned embodiment and embodiment, the so-called lithium rechargeable battery of being represented capacity of negative plates by the capacity component of inserting and deviate from lithium has been described; Yet the present invention can be applicable to: lithium metal secondary battery, and wherein lithium metal is used as negative electrode active material, and by representing capacity of negative plates based on the capacity component of separating out with dissolving lithium; Perhaps following secondary cell, the charging capacity of negative material that wherein can insert and deviate from lithium is less than the charging capacity of positive pole, thereby the capacity of negative pole comprises and inserts and deviate from the capacity component of lithium and separate out capacity component with dissolving lithium, and represented by their summation in an identical manner.
In addition, in above-mentioned embodiment and embodiment, described secondary cell, yet the present invention can be applicable to have folding or lamination is anodal and the secondary cell of the structure of negative pole with winding-structure.In addition, the present invention can be applicable to secondary cells such as so-called Coin shape, coin shape, prismatic.In addition, the present invention not only can be applicable to secondary cell and can also identical mode be applied to primary cell.
Claims (22)
1. positive active material, it comprises:
Lithium composite xoide, described lithium composite xoide comprise lithium (Li) and are selected from least a in cobalt (Co), nickel (Ni) and the manganese (Mn); With
At least a conduct that comprises phosphorus (P) in its surface and be selected from nickel, cobalt, manganese, iron (Fe), aluminium (Al), magnesium (Mg) and the zinc (Zn) coats element.
2. according to the positive active material of claim 1, it comprises:
Core, described core comprise lithium composite xoide and
Superficial layer, described superficial layer is configured at least a portion of described core, and comprises the compound that contains described coating element.
3. according to the positive active material of claim 1, wherein
The lip-deep coating constituent content of described positive active material is greater than the coating constituent content of described positive active material inside, and the content of described coating element reduces to inside from the surface.
4. according to the positive active material of claim 1, wherein
As lithium composite xoide, comprise be selected from Chemical formula 1,2 and 3 the expression compounds at least a:
(Chemical formula 1)
Li
xCo
aM1
bO
2-c
(wherein M1 represents to be selected from least a in nickel, manganese, magnesium, aluminium, boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron, copper (Cu), zinc, molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr) and the silicon (Si), and x, a, b and c value are respectively in following scope: 0.8≤x≤1.2,0.8≤a≤1,0≤b≤0.2 ,-0.1≤c≤0.2)
(Chemical formula 2)
Li
yNi
dM2
eO
2-f
(wherein M2 represents to be selected from least a in cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium, tungsten, zirconium and the silicon, and y, d, e and f value are respectively in following scope: 0.8≤y≤1.2,0.3≤d≤0.98,0.02≤e≤0.7 ,-0.1≤f≤0.2)
(chemical formula 3)
Li
zMn
2-gM3
gO
4-h
(wherein M3 represents to be selected from least a in cobalt, nickel, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and the tungsten, and z, g and h value are respectively in following scope: 0.8≤z≤1.2,0≤g＜1.0 and-0.2≤h≤0.2).
5. according to the positive active material of claim 1, wherein
As coating element, comprise phosphorus and manganese.
6. according to the positive active material of claim 1, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.1mol%～6.0mol% comprises (comprising two-end-point) phosphorus and manganese.
7. according to the positive active material of claim 1, wherein
As coating element, comprise phosphorus and magnesium.
8. according to the positive active material of claim 1, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.1mol%～4.0mol% comprises (comprising two-end-point) phosphorus and magnesium.
9. according to the positive active material of claim 1, wherein
As coating element, comprise phosphorus and aluminium.
10. according to the positive active material of claim 1, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.2mol%～6.0mol% comprises (comprising two-end-point) phosphorus and aluminium.
11. a method of making positive active material, this method may further comprise the steps:
Utilization comprises phosphorus (P) and is selected from least a compound in nickel, cobalt, manganese, iron (Fe), aluminium (Al), magnesium (Mg) and the zinc (Zn), coat the lithium composite xoide particle surface, and they are carried out sintering, described lithium composite xoide comprises lithium (Li) and is selected from least a in cobalt (Co), nickel (Ni) and the manganese (Mn).
12. a battery, it comprises positive pole, negative pole and electrolyte,
Wherein said positive pole comprises the positive active material that comprises lithium composite xoide, and described lithium composite xoide comprises lithium (Li) and is selected from least a in cobalt (Co), nickel (Ni) and the manganese (Mn), and
Described positive active material comprises as the phosphorus (P) that coats element in its surface and is selected from least a in nickel, cobalt, manganese, iron (Fe), aluminium (Al), magnesium (Mg) and the zinc (Zn).
13. according to the battery of claim 12, wherein
Described positive active material comprises: core, and it comprises lithium composite xoide; And superficial layer, it is configured at least a portion of described core and comprises the compound that comprises described coating element.
14. according to the battery of claim 12, wherein
Coating constituent content in the lip-deep positive active material of described positive active material is higher than the coating constituent content of described positive active material inside, and described coating constituent content reduces to inside from the surface.
15. according to the battery of claim 12, wherein
As lithium composite xoide, comprise be selected from Chemical formula 1,2 and 3 the expression compounds at least a:
(Chemical formula 1)
Li
xCo
aM1
bO
2-c
(wherein M1 represents to be selected from least a in nickel, manganese, magnesium, aluminium, boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron, copper (Cu), zinc, molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr) and the silicon (Si), and x, a, b and c value are respectively in following scope: 0.8≤x≤1.2,0.8≤a≤1,0≤b≤0.2 ,-0.1≤c≤0.2)
(Chemical formula 2)
Li
yNi
dM2
eO
2-f
(wherein M2 represents to be selected from least a in cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium, tungsten, zirconium and the silicon, and y, d, e and f value are respectively in following scope: 0.8≤y≤1.2,0.3≤d≤0.98,0.02≤e≤0.7 ,-0.1≤f≤0.2)
(chemical formula 3)
Li
zMn
2-gM3
gO
4-h
(wherein M3 represents to be selected from least a in cobalt, nickel, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and the tungsten, and z, g and h value are respectively in following scope: 0.8≤z≤1.2,0≤g＜1.0 and-0.2≤h≤0.2).
16. according to the battery of claim 12, wherein
As coating element, comprise phosphorus and manganese.
17. according to the battery of claim 12, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.1mol%～6.0mol% comprises (comprising two-end-point) phosphorus and manganese.
18. according to the battery of claim 12, wherein
As coating element, comprise phosphorus and magnesium.
19. according to the battery of claim 12, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.1mol%～4.0mol% comprises (comprising two-end-point) phosphorus and magnesium.
20. according to the battery of claim 12, wherein
As coating element, comprise phosphorus and aluminium.
21. according to the battery of claim 12, wherein
With respect to described lithium composite xoide, superficial layer comprises the coating element that 0.2mol%～6.0mol% comprises (comprising two-end-point) phosphorus and aluminium.
22. according to the battery of claim 12, wherein
Corresponding to every pair of positive pole and negative pole fully the charging state under open circuit voltage in 4.25V～4.6V scope (comprising two-end-point).
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| CN201410242431.9A CN104064729B (en) | 2005-05-17 | 2006-05-11 | Positive active material, the manufacture method and battery of positive active material |
| CN201310502883.1A CN103531765B (en) | 2005-05-17 | 2006-05-11 | Positive electrode active material, method of manufacturing the same and battery |
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| CN201310502883.1A Division CN103531765B (en) | 2005-05-17 | 2006-05-11 | Positive electrode active material, method of manufacturing the same and battery |
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