CN108604680A - Positive electrode active material for nonaqueous electrolyte secondary battery particle and preparation method thereof and non-aqueous electrolyte secondary battery - Google Patents
Positive electrode active material for nonaqueous electrolyte secondary battery particle and preparation method thereof and non-aqueous electrolyte secondary battery Download PDFInfo
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- CN108604680A CN108604680A CN201780008852.7A CN201780008852A CN108604680A CN 108604680 A CN108604680 A CN 108604680A CN 201780008852 A CN201780008852 A CN 201780008852A CN 108604680 A CN108604680 A CN 108604680A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention provides positive electrode active material for nonaqueous electrolyte secondary battery particle.Positive active material particle has layered rock salt structure, includes at least with Li, Ni, Co and Mn lithium composite xoide as main component, the molar ratio of Li/ (Ni+Co+Mn) is 1.09 or more 1.15 or less.The positive active material particle is used as to cathode composition non-aqueous electrolyte secondary battery for anode, by Li, initial charge is carried out under 60 DEG C of environment to 4.6V, horizontal axis represents voltage, the longitudinal axis represent the value i.e. dQ/dV for initial charge capacity being carried out with voltage obtained by differential draw (dQ/dV curves) when, in voltage be peak height in 4.3V or more 4.5V or less ranges be 100mAh/g/V or more 200mAh/g/V or less.
Description
Technical field
The present invention relates to the positive electrode active material for nonaqueous electrolyte secondary battery with high stability layered rock salt structure
Particle and preparation method thereof and non-aqueous electrolyte secondary battery.
Background technology
In recent years, the portability of the electronic equipments such as AV equipment, personal computer, wireless penetration rapidly develop, and are set as these
Standby driving power, to small-sized, light weight and the requirement of the secondary cell with high-energy density improves.In the case, have
Charging/discharging voltage is high, the big advantage of charge/discharge capacity lithium rechargeable battery is received and gazed at.
In the past, the positive active material as the high-energy type lithium rechargeable battery that can be used for having 4V step voltages leads to
The often LiMn of known spinel structure2O4And the LiMnO of rock-salt type structure2、LiCoO2、LiCo1-XNiXO2And LiNiO2
Deng.Wherein, LiCoO2The advantages of be with high voltage and high power capacity, but it is few there are still the supply amount of cobalt raw material and cause to be manufactured into
This high problem and waste battery are in terms of Environmental security the problem of.Therefore, the solid solution of versatility excellent Ni, Co and Mn
Body is ternary system positive active material particle (the basic composition with layered rock salt structure：Li(NixCoyMnz)O2, following phase
Research together) is prevailing.
It is well known that the ternary system positive active material particle of layered rock salt structure can be by by Ni compounds, Coization
Close object, Mn compounds and Li compounds are mixed with regulated proportion, calcined within the temperature range of for example, about 700 DEG C~1000 DEG C and
It obtains.
But the material charging when lithium be detached from when, Ni2+It is converted to Ni3+And ginger-Teller distortion (Jahn- occurs
Teller distortion).Therefore, the row that the lithium ion in crystalline texture is departed from and inserted into being repeated for charge and discharge
So that lattice is flexible, causes crystalline texture unstable and cycle performance is made to deteriorate.In addition, there is also the oxygen released and electrolysis
The problem of liquid reacts and the safety of battery is made to decline.
In the lithium rechargeable battery using ternary system positive active material particle, especially it is required to inhibit anti-at present
Charge/discharge capacity deteriorates and improves the material of battery security caused by multiple charge and discharge.
In order to realize the high security of battery, consider that emphasis is to reduce the ternary system positive active material particle high voltage appearance
Oxygen production quantity and fillibility in region are excellent, have modest size, and further suppress the unstable of crystalline texture
Change.As solution, the proportioning of Li, Ni, Co, Mn compound used in control ternary system positive active material particle has been carried out
Balance, the method for crystallite dimension and size distribution, the method that control calcination temperature obtains powder, same element does not strengthen knot for addition
The method of brilliant binding force, and realize the mesh calibration method etc. by being surface-treated.
So far, as the positive active material particle for improving battery security, it is known that
LiNi0.33Co0.33Mn0.33O2Highly crystalline material (patent document 1).In addition, it is also known that with the lattice caused by charge and discharge cycles
The high-performance stability material (patent document 2) of this small feature of volume change.In turn, it is also known that be generated by adding Ca
The gas of appropriateness is to drive the material (patent document 3) for the purpose of battery safety valve.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-059490 bulletins
Patent document 2：No. 4900888 bulletins of Japanese Patent
Patent document 3：Japanese Unexamined Patent Publication 2014-143108 bulletins
Invention content
Problems to be solved by the invention-
Although as described above, especially needing can be improved the high stability material of battery security as nonaqueous electrolyte at present
Active material for anode of secondary cell, but be not yet received and meet material of sufficient and necessary condition and preparation method thereof.
That is, although above patent document 1 discloses highly crystalline LiNi0.33Co0.33Mn0.33O2And be illustrated, but from reality
Stability is still insufficient from the aspect of, is unable to fully improve the safety of battery.Although in addition, sound in above patent document 2
Claim to change availability stabilizability by reducing the cell volume caused by charge and discharge cycles, but simultaneously for the safety of battery
Without especially record, the safety open to suspicion that whether can fully improve battery.Although in addition, being logical in above patent document 3
The method for specially generating gas and ensureing battery security, but positive active material deficient in stability itself are crossed, practicability is still not
Foot.
The present invention is to complete in view of the above problems, and its object is to obtain the secondary electricity of safe nonaqueous electrolyte
Pond positive active material particle, in addition its purpose also reside in obtained using the positive active material particle it is safe non-aqueous
Electrolyte secondary battery.
The solution to the problem-
In order to achieve the above objectives, in the present invention, by least using Li, Ni, Co and Mn as main component, Li/ (Ni+Co+
Mn molar ratio) is that 1.09 or more 1.15 lithium composite xoides below constitute positive active material particle.
Specifically, positive electrode active material for nonaqueous electrolyte secondary battery particle of the present invention is with bedded rock
Salt structure, including at least with the positive active material particle of Li, Ni, Co and Mn lithium composite xoide as main component, it is special
Sign is that the molar ratio of Li/ (Ni+Co+Mn) is 1.09 or more 1.15 or less；By the positive active material particle for just
Li is used as cathode composition non-aqueous electrolyte secondary battery by pole, is carried out initially with the current density of 16mA/g under 60 DEG C of environment
Charge to 4.6V, horizontal axis represents voltage, the longitudinal axis represent with voltage to initial charge capacity carry out value i.e. dQ/dV obtained by differential into
Row draw (dQ/dV curves) when, in voltage be peak height in 4.3V or more 4.5V or less ranges be 100mAh/g/V or more
200mAh/g/V or less.
Positive active material particle of the present invention has above structure, thus has high stability, can be used for manufacturing
Safe battery.
Have been generally acknowledged that Li2MnO3Region (domain) it is critically important for the lattice stability of ternary system complex oxide, such as
Fruit Li contents are less than above range, then Li2MnO3Amount of area reduce stability reduce.On the other hand, if Li composite oxides
In there are a large amount of Li2MnO3, then when charging to the high voltage of 4.5V or more, a large amount of Li2MnO3Decompose and cause the generation of oxygen.
As a result, being full of by oxygen in battery, battery is possible to generate heat and explode caused by high voltage.
But this time the inventors discovered that, using the Li composite oxides with above structure as active material be used for just
Li is formed button cell (coin cell) by pole, with 0.2C charge rates (Capacity under 60 DEG C of environment
Rate when) (current density 16mA/g) carries out initial charge to 4.6V, although the Li containing above-mentioned molar ratio, in dQ/dV
In curve, it is meant that there are Li in positive active material2MnO3Peak value there is extremely low value.That is, positive-active of the present invention
Even if material grains are in the case where charging to high voltage, and the suppressed height of generation of the oxygen from positive active material is steady
Qualitative activity substance can obtain safe battery by using the positive active material particle.
Preferably, positive active material particle of the present invention is solved by the special Wald of X-ray diffraction (XRD diffraction)
Analysing the crystallite dimension (crystallite size) obtained by (Rietveld analysis, hereinafter referred to as Rietveld are parsed) is
400nm or more 1000nm hereinafter, average aggregate particle size (D50) be 3 μm or more 7 μm hereinafter, and (D90-D10)/D50 0.54
In the range of~0.60.
The stability of particle itself will not decline as a result, and can improve fillibility.
The preparation method characteristic of positive electrode active material for nonaqueous electrolyte secondary battery particle of the present invention is, incites somebody to action
Using Ni, Co and Mn complex chemical compound as main component as precursor, mixed lithiated conjunction object makes Li/ in the precursor
(Ni+Co+Mn) molar ratio reaches 1.09 or more 1.15 ranges below, then in oxidizing atmosphere, 950 DEG C or more
It is calcined at 1050 DEG C of temperature below, obtains the composite oxides containing Li, Ni, Co and Mn.
If calcined at a temperature of less than 950 DEG C, stability can be damaged.In addition, if in the temperature higher than 1050 DEG C
The lower calcining of degree, then granular grows excessively will produce crackle etc. and cause unstable.Therefore, according to positive-active of the present invention
The preparation method of material grains can obtain the above-mentioned positive active material particle with high stability.
Preferably, in the preparation method of positive active material particle of the present invention, can confirm the Ni of precursor with
The molar ratio Ni of Co and Mn：Co：Mn is 1:1:1, Ni mainly exists with the state of nickel hydroxide, and Co is with hydroxyl cobalt hydroxide or oxygen
The state for changing cobalt exists, and additionally, there may be NiMn2O4Spinelle.
Li can be made to be easy progress with reacting for precursor as a result, obtain the positive active material particle of high stability.
Preferably, in the preparation method of positive active material particle of the present invention, the average secondary grain of precursor
Diameter D50 is 3.5 μm or more 6.5 μm of ranges below, and tap density is 1.65g/ml or more.
The reaction is set to reach granular center portion with reacting for precursor thus, it is possible to sufficiently promote Li in calcination process,
And fully obtain highdensity positive active material particle.
Non-aqueous electrolyte secondary battery of the present invention is characterized in that, above-mentioned non-aqueous electrolyte secondary battery has been used to use
Positive active material particle.
According to non-aqueous electrolyte secondary battery of the present invention, due to the use of above-mentioned positive active material, therefore such as
It is above described to improve safety.
The effect of invention-
Positive electrode active material for nonaqueous electrolyte secondary battery particle of the present invention shows high security, therefore suitable
It shares and makees positive electrode active material for nonaqueous electrolyte secondary battery.
Description of the drawings
Fig. 1 is (dQ/dV curves) figure, and horizontal axis represents voltage, the longitudinal axis represents and carries out differential to initial charge capacity with voltage
Value, that is, dQ/dV of gained.
Fig. 2 is the chart of the XRD diffraction patterns of the precursor for the positive active material particle for indicating that embodiment is related to.
Specific implementation mode
Hereinafter, embodiments of the present invention will be described.It is merely illustrative in the illustrative in nature of following preferred embodiment,
It is not intended to be limiting of the invention, the purposes of the usability methods of the present invention or the present invention.
First, positive electrode active material for nonaqueous electrolyte secondary battery particle one embodiment of the present invention being related into
Row explanation.
Positive active material particle of the present embodiment have layered rock salt structure, by least contain Li, Ni, Co and
The composite oxides of Mn are constituted.
Mole that the Li content ranges of positive active material particle of the present embodiment are indicated with Li/ (Ni+Co+Mn)
Ratio is 1.09~1.15.Have been generally acknowledged that Li2MnO3Region it is critically important for the lattice stability of Li composite oxides, in Li
Content is less than the Li in the case of above range, being randomly present in the Li composite oxides2MnO3Amount is reduced.As a result, due to
The stability of Li composite oxides reduces, therefore the penalty of positive active material particle.On the other hand, it is more than in Li contents
In the case of above range, it is formed by Li2MnO3Amount is excessive, causes to release a large amount of oxygen when high voltage.As a result, making battery
Safety reduce.The molar ratio more preferably indicated with Li/ (Ni+Co+Mn) is 1.10~1.15.
In addition, in positive active material particle of the present embodiment, by the positive active material particle for anode,
Li is used as cathode and forms non-aqueous electrolyte secondary battery, initial charge is carried out with the current density of 16mA/g under 60 DEG C of environment
To 4.6V, horizontal axis represents voltage, the longitudinal axis is represented the value i.e. dQ/dV carried out obtained by differential to initial charge capacity with voltage and painted
In voltage be peak height in 4.3V or more 4.5V or less ranges it is 100mAh/g/V or more 200mAh/g/ when scheming (dQ/dV curves)
V or less.
When drawing above-mentioned dQ/dV curves, which shows battery capacity occur in the voltage range present in peak.This
It is secondary, the inventors discovered that, in various experiments in the dQ/dV curves of aforementioned button cell, between 4.3V~4.5V peak there are tables
There are Li in the bright lattice between 4.3V~4.5V in positive active material2MnO3.That is, the inventors discovered that dQ/ can be utilized
DV curves are to Li2MnO3Amount is quantified.
If usual Li2MnO3Largely exist in the Li composite oxides, then battery is made as cathode in Li and charged to
When the high voltage of 4.5V or more, Li can be caused2MnO3It decomposes and generates oxygen.As a result, being full of by oxygen in battery, battery has can
Can caused by high voltage anode fever due to explode.
The present invention's focuses on, although easily being formed with the molar ratio that Li/ (Ni+Co+Mn) is indicated in improving
Li2MnO3Situation, but the peaks dQ/dV can be reduced in the range of 4.3V~4.5V.The consideration of its reason is randomly to exist
In the state of, usually there is the Li of stacking fault2MnO3Crystallinity improve, result can cause to inactivate.By making Li2MnO3's
Activity inactivation, even if can also inhibit the generation of oxygen in high voltage, as a result can reduce when battery is made and occur to the maximum extent
The possibility of explosion.
In addition, inventors believe that, obtain the positive-active by being calcined at a high temperature of 950 DEG C~1050 DEG C
Substance, to make the Li of the inactivation2MnO3In the hexagonal crystal of the random lamellar compound for being present in the present invention, thus generate to layer
The pillar effect (pillar effect) in shape halite compounds region forms the positive active material that can show high stability.
It based on the above situation, is studied through the present inventor, the results showed that positive active material particle of the present invention is in dQ/
In dV curves, the maximum value at the peak occurred between 4.3V~4.5V is preferably 100mAhg-1·V-1~200mAhg-1·V-1、
More preferably 120mAhg-1·V-1~190mAhg-1·V-1, even more preferably be 120mAhg-1·V-1~
180mAh·g-1·V-1。
In addition, the positive active material particle in present embodiment can be contained in the form of for example adulterating, being coated with Mg,
The metallic elements such as Al, Ti, V, Fe, Ga, Sr, Y, Zr, Nb, Mo, Ru, In, Sn, Ta, W and Bi.By making positive active material
Contain these metallic elements in particle, cycle performance, charge and discharge rate performance and safety can be improved when battery is made.
Furthermore it is preferred that positive active material particle of the present embodiment parses institute by the Rietveld of XRD diffraction
The crystallite dimension obtained is 400nm~1000nm.The growth crystallized when crystallite dimension is less than 400nm is insufficient and safety is caused to be disliked
Change.Primary particle can be caused to increase if crystallite dimension is more than 1000nm, it is cracked equal and become unstable.Crystallite dimension
More preferably 500nm~950nm.
In addition, the average aggregate particle size (D50) of positive active material particle of the present embodiment is 3 μm~7 μm, simultaneously
And (D90-D10)/D50 is in the range of 0.54~0.60.It should be noted that (D90-D10)/D50 is the finger of breadth of particle size distribution
Mark, indicates the degree of scatter of size distribution.When average aggregate particle size is less than 3 μm, using the electrode active material as agglutinating particle
It is made unstable when battery.In addition, when average aggregate particle size is more than 7 μm, output performance, cycle performance deteriorate and damage and stablize
Property.Moreover, in order to improve fillibility, need that size distribution is made to broaden, positive active material particle of the present embodiment
(D90-D10)/D50's ranges preferably from 0.55~0.58.
Then, positive electrode active material for nonaqueous electrolyte secondary battery particle one embodiment of the present invention being related to
Preparation method illustrates.
It, first, will in order to prepare positive electrode active material for nonaqueous electrolyte secondary battery particle of the present embodiment
It is mixed with lithium compound using Ni, Co and Mn complex chemical compound as main component as precursor so that with Li/ (Ni+Co+Mn)
The molar ratio of expression reaches 1.09~1.15 range.Then, at a temperature of in oxidizing atmosphere, 950 DEG C~1050 DEG C
Mixture is calcined, it is hereby achieved that the Li composite oxides containing Li, Ni, Co and Mn.
The co-precipitation that at least precursor complex chemical compound containing Ni, Co and Mn in the present invention can be reacted by wet type
Deng and obtain, specifically, by dissolved with sulfuric acid Ni, sulfuric acid Co, sulfuric acid Mn up to 1.5mol% solution and 0.3mol% it is severe
Property sodium solution and 0.1mol ammonia solutions simultaneously instill carry out coprecipitation reaction, reactant is obtained by overflow (overflow), so
It washes afterwards, is dry, obtaining the complex chemical compound.It is 0.18wt% hereinafter, the parts Na are 300ppm hereinafter, simultaneously that it, which remains S portion,
And the total impurities amount including moisture is 0.35wt% or less.If impurity level is more, it is likely that forming the compound chemical combination of Li
It is difficult to be synthesized when object, or safety can be damaged when battery is made.
Furthermore it is preferred that in drying process after wet type reaction, precursor is dried to not generating NiMnO3Degree.
As a result, it is possible to easily fully be reacted with Li in synthesis, the high positive active material particle of stability is obtained.It should say
Bright, Co can be hydroxyl cobalt hydroxide at this time, or be alternatively cobalt oxide.Furthermore it is also possible to which there are NiMn2O4Etc spinelle
Compound.
Alternatively, it is also possible to add other metallic elements during wet type is reacted.The metallic element added can be deposited
It is in hydroxide particles, can also exist on the outer rim of hydroxide particles.As the type of addible metallic element,
Mg, Al, Ti, V, Fe, Ga, Sr, Y, Zr, Nb, Mo, Ru, In, Sn, Ta, W and Bi etc. can be enumerated.
Preferably, the model that the average aggregate particle size (D50) of the precursor as obtained by wet type operation is 3.5 μm~6.5 μm
It encloses, tap density 1.65g/cm3More than.By making average aggregate particle size within the above range, can in calcination process with
Li compounds are fully reacted when reacting to central part, and Li is made2MnO3Highly crystalline region randomly exist.In addition, it is also contemplated that if upper
Tap density is stated, then can fully obtain highdensity positive active material particle when being reacted with Li compounds.
It is not particularly limited as the lithium compound used in the present invention, various lithium salts can be used, such as hydrogen can be enumerated
Lithia monohydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide, lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lactic acid
Lithium, lithium oxalate, lithium phosphate, pyruvic acid lithium, lithium sulfate and lithia etc., wherein preferably lithium carbonate.
Then, the anode for having used positive active material is illustrated, which includes the one of the present invention
The positive electrode active material for nonaqueous electrolyte secondary battery particle that embodiment is related to.
Using containing positive active material particle of the present embodiment anode manufacture secondary cell by it is above-mentioned just
Pole, cathode and electrolyte are constituted.
It is living to anode according to well-established law when manufacture contains the anode of positive active material particle of the present embodiment
Property material grains in addition and hybrid conductive agent and adhesive.As conductive agent, preferably acetylene black, carbon black and graphite etc.,
It is preferably polytetrafluoroethylene (PTFE) and Kynoar etc. as adhesive.
It is used as negative electrode active material in the present invention, lithium metal, lithium/aluminium alloy, lithium/tin alloy, graphite or black can be used
Lead etc..
In addition, the solvent as electrolyte, can use the group in addition to ethylene carbonate (EC) and diethyl carbonate (DEC)
Also include in the ethers such as carbonates, the dimethoxy-ethanes such as propylene carbonate (PC), dimethyl carbonate (DMC) other than conjunction
At least one organic solvent.
It in turn, can will be in addition to lithium lithium phosphate (LiPF as electrolyte6) other than, also lithium perchlorate
(LiClO), tetrafluoride lithium borate (LiBF4) etc. at least one of lithium salts be dissolved in above-mentioned solvent and use.
Use the secondary electricity of nonaqueous electrolyte of the anode manufacture containing positive active material particle of the present embodiment
When carrying out overcharge test according to aftermentioned evaluation method, the peak height of 4.3V~4.5V is 100mAhg in pond-1·V-1~
200mAh·g-1·V-1。
When using positive active material particle of the present invention, by reaching above-mentioned peak height, it can not only make Li2MnO3
Highly crystalline region be randomly present in the lattice of positive active material, realize stratiform halite compounds stabilisation, but also
Li can be come from by being greatly decreased2MnO3Oxygen release property to ensure safety.
[embodiment]
The representative embodiment of the present invention is as described below.
The composition of positive active material particle determines as follows：1.0g samples are dissolved by heating in 20% hydrochloric acid solution of 25ml
In, be transferred in 100ml measuring bottles after cooling, pure water be added and is made adjustment liquid, in measurement using ICAP (Optima8300,
PerkinElmer Inc. systems) each element is quantified.
The calculating of the tap density of the precursor of positive active material particle carries out as follows：40g samples are weighed, 50ml is put into
In graduated cylinder, using tap density meter (tap denser, SEISHIN ENTERPRISE CO., LTD. system) according to vibration
(tapping) 1200 times when volume calculate reading tap density.
S contents use " HORIBA CARBON/SULFUR ANALYZER EMIA-320V (HORIBA Scientific) "
It is measured.
The identification of the compound phase of positive active material particle carries out as follows：Using X-ray diffraction device (SmartLab,
Rigaku Corporation systems), 1.2 °/min step-scans are carried out with 0.02 ° of 2 θ of step-length pair/θ ranges for being 10 °~90 °
(Step-scan)。
Average aggregate particle size (D50), (D90-D10)/D50 values refer to using laser type particle size distribution device
MICROTRAC HRA (NIKKISO CO., LTD. system), by the average grain diameter for the volume reference that wet type laser method measures.
The calculating of the crystallite dimension of positive active material particle carries out as follows：Using X-ray diffraction device (SmartLab,
Rigaku Corporation systems), slit (slit) is 2/3 degree, is carried out with 0.02 ° of 2 θ of step-length pair/θ ranges for being 10 °~90 °
1.2 °/min step-scans.Then, Rietveld analytical Calculations are carried out by using text data (text data) and goes out crystallite ruler
It is very little.
It should be noted that in Rietveld parsings, value when using Rwp be 13~20, S values are 1.3 or less.
Hereinafter, about positive active material particle of the present invention, comment using 2032 type button cells to carry out battery
The method and result of valence illustrate.
It is following to make for the button cell that cell evaluation is related to.First, using 90 weight % of composite oxides as aftermentioned
Positive active material particle powder that each embodiment and comparative example illustrated is related to, 3 weight % of acetylene black, 3 weight % of graphite make
It is mixed as adhesive for conductive material, 4 weight % of the Kynoar being dissolved in N-Methyl pyrrolidone, is then applied
It is distributed in Al metal foils, it is dry at 120 DEG C.After the sheet material is punched into 14mm Φ, with 1.5t/cm2Crimping is carried out for just
Pole.Cathode is the lithium metal for 500 μm of thickness for being punched into 16mm Φ, and electrolyte uses the LiPF dissolved with 1mol/L6EC (carbon
Sour ethyl) with DMC (dimethyl carbonate) with volume ratio 1:2032 type button cells are made in 2 solution mixed.
Horizontal axis represents voltage, the longitudinal axis represents the value i.e. song of dQ/dV carried out to initial charge capacity with voltage obtained by differential
Line chart (dQ/dV curves) is drawn as follows：By above-mentioned button cell group with 0.2C charge rate (current densities in the environment of 60 DEG C
Charging density 16mA/g) carries out initial charge to 4.6V, by voltage at this time for horizontal axis, with voltage to initial charge capacity
It carries out value, that is, dQ/dV obtained by differential and is used for the longitudinal axis, the curve graph that voltage is 4.2V~4.6V ranges is made.
Then, the preparation method for the positive active material particle being related to each embodiment and comparative example illustrates.
Embodiment 1
With the molar ratio computing Ni of each element：Co：Mn=1:1:1 weighs sulfuric acid Ni, sulfuric acid Co and sulfuric acid Mn, by above-mentioned wet
Formula reaction is allowed to be co-precipitated.It washed, dried, obtain (Ni0.33Co0.33Mn0.33) composite oxide particle (precursor).It should
The average aggregate particle size of precursor is 4.8 μm, and residual S amounts are 0.13wt%, and residual Na amounts are 187ppm, and total impurities amount is
0.25wt%, tap density 1.83g/ml.
After obtaining precursor as described above, the precursor is mixed 1 hour with lithium carbonate with mortar so that Li/ (Ni+Co+
Mn) reach 1.11 with molar ratio computing, obtain uniform mixture.Gained mixture 50g is put into alumina crucible, is being aoxidized
It is kept for 5 hours in property atmosphere, at 980 DEG C, thus obtains Li1.11(Ni0.33Co0.33Mn0.33)O2Positive active material particle.
Embodiment 2
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.12 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 980 DEG C, thus obtain Li1.12(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Embodiment 3
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.14 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 1000 DEG C, thus obtain Li1.14(Ni0.33Co0.33Mn0.33)
O2Positive active material particle.
Embodiment 4
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.12 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 990 DEG C, thus obtain Li1.12(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Embodiment 5
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.10 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 950 DEG C, thus obtain Li1.10(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Embodiment 6
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.13 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 1020 DEG C, thus obtain Li1.13(Ni0.33Co0.33Mn0.33)
O2Positive active material particle.
Embodiment 7
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.10 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 970 DEG C, thus obtain Li1.10(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Embodiment 8
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.12 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 950 DEG C, thus obtain Li1.12(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Comparative example 1
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.16 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 1010 DEG C, thus obtain Li1.16(Ni0.33Co0.33Mn0.33)
O2Positive active material particle.
Comparative example 2
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.16 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 970 DEG C, thus obtain Li1.16(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Comparative example 3
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.18 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 980 DEG C, thus obtain Li1.18(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Comparative example 4
Using the precursor of the complex chemical compound synthesized by above-described embodiment 1, the precursor is mixed with lithium carbonate with mortar
It closes 1 hour so that Li/ (Ni+Co+Mn) reaches 1.12 with molar ratio computing, obtains uniform mixture.By gained mixture 50g
It is put into alumina crucible, is kept for 5 hours in air atmosphere, at 930 DEG C, thus obtain Li1.12(Ni0.33Co0.33Mn0.33)O2
Positive active material particle.
Positive active material particle for each embodiment and comparative example that obtain as described above, measures according to the above method
Crystallite dimension, average aggregate particle size (D50) and (D90-D10)/D50, and then using each embodiment and compare according to the above method
Button cell is made in the positive active material particle of example, draws dQ/dV curves as described above, determines within the scope of 4.3V~4.5V
Peak value.The results are shown in the following table 1, in addition, Fig. 1 shows the dQ/dV curves of embodiment 1, comparative example 1 and comparative example 3.In turn,
Fig. 2 shows the precursors of the positive active material particle to embodiment 1 to carry out XRD diffraction to identify the knot of precursor compound phase
Fruit.
[table 1]
As shown in Figure 1, having used the button-type battery of the positive active material particle of embodiment 1 in aforementioned dQ/dV curves
In, peak is located at 100mAh/g/V or more 200mAh/g/V ranges below in the range of 4.3V~4.5V, shows low value.With this
Relatively, it is known that comparative example 1 and comparative example 3 are in dQ/dV curves, and peak is more than 200mAh/g/V in the range of 4.3V~4.5V.
In addition, as shown in table 1, other than embodiment 1, the molar ratio of Li/ (Ni+Co+Mn) is 1.09 or more 1.15
Below and calcination temperature is 950 DEG C~1050 DEG C of embodiment 2~8 in dQ/dV curves, 4.3V or more 4.5V or less ranges
Interior peak height is 100mAh/g/V or more 200mAh/g/V or less.That is, by using the positive active material of Examples 1 to 8
Grain, can obtain safe battery.
In addition, as shown in Figure 2, it is known that in the precursor of the positive active material particle of embodiment 1, as out-phase Ni with hydrogen
The state of nickel oxide exists, Co exists with the state of hydroxyl cobalt hydroxide, and there are NiMn2O4.Therefore, the precursor and Li
Reaction be easy to carry out, result can obtain the high positive active material particle of stability.
Industrial applicability-
Positive electrode active material for nonaqueous electrolyte secondary battery particle of the present invention can have when battery is made
High security, therefore it is suitable for positive electrode active material for nonaqueous electrolyte secondary battery.
Claims (6)
1. positive electrode active material for nonaqueous electrolyte secondary battery particle, be with layered rock salt structure, include at least with Li,
The positive active material particle of Ni, Co and Mn lithium composite xoide as main component, which is characterized in that
The molar ratio of Li/ (Ni+Co+Mn) be 1.09 or more 1.15 hereinafter,
The positive active material particle is used as to cathode composition non-aqueous electrolyte secondary battery for anode, by Li, at 60 DEG C
Initial charge is carried out under environment to 4.6V, horizontal axis represents voltage, the longitudinal axis represents and carries out differential institute to initial charge capacity with voltage
Value, that is, dQ/dV when drawing dQ/dV curve graphs, in voltage be peak height in 4.3V or more 4.5V or less ranges be 100mAh/
G/V or more 200mAh/g/V or less.
2. positive active material particle according to claim 1, which is characterized in that
Crystallite dimension as obtained by the parsing of the special Wald of X-ray diffraction is 400nm or more 1000nm hereinafter, average secondary grain
Diameter (D50) be 3 μm or more 7 μm hereinafter, and (D90-D10)/D50 in the range of 0.54~0.60.
3. the preparation method of positive active material particle is the preparation side of positive active material particle described in claim 1
Method, which is characterized in that
Will be using Ni, Co and Mn complex chemical compound as main component as precursor, mixed lithiated is closed object and is made in the precursor
The molar ratio for obtaining Li/ (Ni+Co+Mn) reaches 1.09 or more 1.15 ranges below, then in oxidizing atmosphere, 950 DEG C
It is calcined above 1050 DEG C of temperature below, obtains the composite oxides containing Li, Ni, Co and Mn.
4. the preparation method of positive active material particle according to claim 3, which is characterized in that
The Ni of the precursor：Co：The molar ratio of Mn is 1:1:1, Ni exists with the state of nickel hydroxide, and Co is with hydroxyl hydroxide
The state of cobalt or cobalt oxide exists, and additionally, there may be NiMn2O4。
5. the preparation method of positive active material particle according to claim 4, which is characterized in that
The average aggregate particle size D50 of the precursor is 3.5 μm or more 6.5 μm of ranges below, tap density 1.65g/ml
More than.
6. non-aqueous electrolyte secondary battery, it uses positive active material particles as claimed in claim 1 or 2.
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| JP2016-031406 | 2016-02-22 | ||
| JP2016031406 | 2016-02-22 | ||
| JP2016201260A JP6053982B1 (en) | 2016-02-22 | 2016-10-12 | Positive electrode active material particles for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| JP2016-201260 | 2016-10-12 | ||
| PCT/JP2017/005446 WO2017145888A1 (en) | 2016-02-22 | 2017-02-15 | Positive electrode active material particles for non-aqueous electrolyte secondary battery, production method therefor, and non-aqueous electrolyte secondary battery |
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| JP (1) | JP6053982B1 (en) |
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| WO2020218826A1 (en) * | 2019-04-22 | 2020-10-29 | 주식회사 엘지화학 | Device and method for determining differential voltage curve of battery, and battery pack comprising device |
| CN113461058A (en) * | 2021-07-15 | 2021-10-01 | 河南理工大学 | Cathode material Li with disordered rock salt structure1.3Mo0.3V0.4O2Method of synthesis of |
| CN113764656A (en) * | 2020-06-04 | 2021-12-07 | Sk新技术株式会社 | Positive electrode active material for lithium secondary battery |
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| JP6669920B1 (en) * | 2018-09-21 | 2020-03-18 | 株式会社田中化学研究所 | Positive electrode active material for secondary battery and method for producing the same |
| JP7228113B2 (en) * | 2018-11-13 | 2023-02-24 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
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| JP2017152359A (en) | 2017-08-31 |
| JP6053982B1 (en) | 2016-12-27 |
| TW201737543A (en) | 2017-10-16 |
| WO2017145888A1 (en) | 2017-08-31 |
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