CN107210440A - Positive active material, positive pole and lithium secondary battery comprising the material - Google Patents
Positive active material, positive pole and lithium secondary battery comprising the material Download PDFInfo
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- CN107210440A CN107210440A CN201680007307.1A CN201680007307A CN107210440A CN 107210440 A CN107210440 A CN 107210440A CN 201680007307 A CN201680007307 A CN 201680007307A CN 107210440 A CN107210440 A CN 107210440A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to the positive active material for lithium secondary battery for including the lithium-nickel-manganese-cobalt oxide represented with chemical formula 1, the content of the nickel for the Ni-Mn-Co-O compound that positive active material of the invention is included is more than manganese, therefore, it is possible to suppress Ni2+Generation, is prevented because of Ni2+The reduction of chemical property caused by being moved to lithium layer, and it can suitably adjust the content of manganese and cobalt and realize raising and the high power capacity of output as needed, therefore be effectively used for the preparation of positive electrode for lithium secondary battery and the preparation of the lithium secondary battery comprising the positive pole.
Description
Technical field
[the mutual reference with related application]
This application claims excellent based on 2 months 2015 korean patent applications filed in 27 days the 10-2015-0028378th
First weigh, the full content disclosed in related korean patent application document will be used as the part in this specification.
[technical field]
The present invention relates to can realize to improve output with the positive active material for lithium secondary battery of high power capacity, comprising the thing
The positive pole and lithium secondary battery of matter.
Background technology
With the technological development and the increase of demand to mobile device, to the demand of the secondary cell as the energy drastically
Increase, and in this secondary cell, present high-energy-density and operating potential, have extended cycle life, the lithium that self-discharge rate is low
Secondary cell is popularized and is widely used.
Also, recently as to the concern of environmental problem increase, pair the main cause as atmosphere pollution can replaced
One of gasoline vehicle, diesel vehicle etc. using the vehicle of fossil fuel electric automobile (EV), mixed power electric car
Etc. (HEV) much studied.
The power source that this electric automobile (EV), mixed power electric car (HEV) etc. are used is ni-mh metal (Ni-MH)
Secondary cell, or high-energy-density, high discharge voltage and output stability lithium secondary battery.Lithium secondary battery is being used in electricity
In the case of electrical automobile, there should be high-energy-density and the characteristic exported greatly can be played in a short time, and need severe
Under the conditions of use more than 10 years, therefore, be necessarily required to it is a kind of than existing small-sized lithium secondary battery especially excellent stability and
The characteristic of long lifespan.Also, according to the condition of work of vehicle, for electric automobile (EV), mixed power electric car (HEV) etc.
Secondary cell need excellent multiplying power (rate) characteristic and power (power) characteristic.
Currently, the positive active material of usually used lithium rechargeable battery has layer structure (layered
Structure LiCoO)2Deng the cobalt/cobalt oxide containing lithium, layer structure LiNiO2Deng the nickel oxide containing lithium, spinelle
The LiMn of crystal structure2O2Deng the Mn oxide containing lithium etc..
LiCoO2Many excellent physical property with excellent cycle characteristics etc., thus it is currently used in the majority, but security
It is low, and cause to make it the problem of as caused by the resource limit of the cobalt of raw material in price as the dynamic of the fields such as electric automobile
A large amount of uses are carried out in power source has limitation.Also, to LiNiO2For, it is difficult with reasonable because of the characteristic of its preparation method
Expense be applied to actual a large amount of production technologies.
On the other hand, LiMnO2、LiMn2O4Deng the advantage of lithium manganese oxide be using raw material resources are abundant and environmental protection
Manganese, therefore conduct can replace LiCoO2Positive active material get most of the attention, but lithium manganese oxide has also the drawback that, for example, circulate
Characteristic etc. is bad.Specifically, LiMnO2Shortcoming be：Initial capacity is small, reach specified volume untill need tens of time fill
Discharge cycles.Also, LiMn2O4Have as a drawback that：With continuing for circulation, capacity is seriously reduced, high especially more than 50 DEG C
Because electrolyte decomposition, dissolution of manganese etc. cause cycle characteristics to drastically reduce under temperature state.
On the other hand, LiNiO2Class positive active material has as a drawback that：Become with the volume of charge and discharge cycles
Change, occur phase transformation drastically in crystalline texture, stability is drastically reduced in the case of in air and moisture.But with
Above-mentioned cobalt type oxide is compared, cheap and high discharge capacity is shown in the case where being charged as 4.3V.
Thus, in order to solve LiNiO2The shortcoming of class positive active material, it is proposed that utilize other transition metal such as manganese, cobalt
Replace the lithium transition-metal oxide of the form of a part for nickel, for example, having carried out respectively by 1:1 or 1:1:1 ratio is mixed
Closing the oxidate for lithium of nickel-manganese and nickel-cobalt-manganese is used for the trial and research of positive active material.
Compared with the battery manufactured in the way of each transition metal is used alone, in the way of mixed Ni, cobalt or manganese
Though increased come many physical property of positive active material prepared, there is still a need for improving in terms of high-rate characteristics, also,
In the case of the equivalent identical of nickel and manganese, with Mn4+Ion induction Ni2+The Ni that the mode of the formation of ion is formed2+To Li sites
(site) move and cause chemical property to reduce.
Overcome or minimized accordingly, it would be desirable to develop and various positive active materials are had the disadvantage that, and be used as electricity
The nickel-manganese of the lithium with layer structure-cobalt based composite oxide of the excellent active material of pond performance balance.
The content of the invention
The invention technical problem to be solved
It is an object of the present invention to provide following positive active material for lithium secondary battery：To adjust the content of manganese and cobalt
Mode come realize improve output and high power capacity.
Another object of the present invention is to there is provided the positive electrode for lithium secondary battery for including above-mentioned positive active material.
Another object of the present invention is to there is provided the lithium secondary battery for including above-mentioned positive electrode for lithium secondary battery.
Solve the means of technical problem
According to above-mentioned purpose, the present invention is provided with the positive active material for lithium secondary battery constituted as follows.
(1) positive active material for lithium secondary battery of the lithium nickel-manganese-cobalt/cobalt oxide represented with following chemical formula 1 is included,
Chemical formula 1：
LiaNixMnyCozO2,
In above-mentioned chemical formula 1,1≤a≤1.2, x=1-y-z, 0 ＜ y ＜ 1,0 ＜ z ＜ 1, x ＞ y, z=ny or y=nz,
N ＞ 1.
(2) positive active material for lithium secondary battery according to above-mentioned (1), above-mentioned x has 0.4≤x≤0.95
Value.
(3) positive active material for lithium secondary battery according to above-mentioned (1) or above-mentioned (2), above-mentioned lithium nickel-manganese-
In the above-mentioned nickel that cobalt/cobalt oxide is included, the nickel of the amount corresponding with the content of above-mentioned manganese is with Ni2+Form is present.
(4) positive active material for lithium secondary battery according to above-mentioned (3), in above-mentioned lithium nickel-manganese-cobalt/cobalt oxide institute
Comprising above-mentioned nickel in, more than the content corresponding with the content of above-mentioned manganese amount nickel with Ni3+Form is present.
(5) positive active material for lithium secondary battery according to any one of above-mentioned (1) to above-mentioned (4), above-mentioned
Ni has the Average oxidation number bigger than+2.
(6) positive active material for lithium secondary battery according to any one of above-mentioned (1) to above-mentioned (5), except upper
The Average oxidation number of Ni, Mn and Co outside Li are stated more than 3.0.
(7) positive active material for lithium secondary battery according to any one of above-mentioned (1) to above-mentioned (6), above-mentioned
Lithium nickel-manganese-cobalt/cobalt oxide includes：Transition metal-oxide skin(coating) (MO layers) comprising transition metal and lithium-oxygen comprising lithium
Compound layer (reversible lithium layer), above-mentioned MO layers includes Ni2+And Ni3+, above-mentioned Ni2+In a part be embedded in above-mentioned reversible lithium layer.
(8) positive active material for lithium secondary battery according to above-mentioned (7), is included as in above-mentioned reversible lithium layer
Whole Li sites in Ni2+The ratio of institute mass point, the Ni of embedded above-mentioned reversible lithium layer2+Content for 5 molar percentages with
Under.
(9) positive active material for lithium secondary battery according to above-mentioned (7), base is used as using the gross weight of nickel ion
Standard, above-mentioned Ni2+Weight be 0.1 percentage by weight to 2 percentage by weights.
(10) positive active material for lithium secondary battery according to any one of above-mentioned (1) to above-mentioned (8), above-mentioned
N is 2 to 5 natural number.
Also, (11) of the invention are provided comprising the secondary lithium batteries described in any one of above-mentioned (1) to above-mentioned (10)
The positive electrode for lithium secondary battery of positive active material.
And then, (12) of the invention, which are provided, includes the lithium secondary battery of above-mentioned positive electrode for lithium secondary battery.(13) above-mentioned lithium two
Primary cell can be used as the power supply of electric automobile, mixed power electric car or plug-in hybrid electric automobile.
The effect of invention
Lithium nickel-manganese-cobalt/cobalt oxide that the positive active material for lithium secondary battery of the present invention is included, the content ratio of its nickel
Manganese is more, therefore, it is possible to suppress Ni2+Generate and prevent because of Ni2+The reduction of chemical property caused by being moved to lithium layer, and pass through
The content of appropriate regulation manganese and cobalt and raising and the high power capacity for realizing output as needed, therefore it is effectively used for the secondary electricity of lithium
The preparation of pond positive pole and the preparation of lithium secondary battery comprising the positive pole.
Brief description of the drawings
Fig. 1 and Fig. 2 is respectively the scanning electron of the lithium nickel-manganese-cobalt/cobalt oxide prepared in embodiment 1 and comparative example 1
Microscope (SEM) photo.
Fig. 3 is the cycle characteristics evaluation experimental knot of lithium secondary battery for showing to prepare respectively in embodiment 5 and comparative example 4
The chart of fruit.
Fig. 4 is the lithium secondary battery for showing to prepare respectively into comparative example 6 in embodiment 6 to embodiment 8 and comparative example 4
The chart of cycle characteristics evaluation experimental result.
Fig. 5 is the utilization HPPC (hybrid powers of lithium secondary battery for showing to prepare respectively in embodiment 5 and comparative example 4
Pulse ability characteristics) lithium secondary battery resistance measurement experimental result chart.
Embodiment
Hereinafter, in order to improve the understanding of the present invention, the present invention will be described in more detail.
Term or word are not limited to the lexical or textual analysis in dictionary, hair used in this specification and the claimed scope of invention
A person of good sense in optimal method to the invention of oneself in order to illustrate, and concept that can be suitably to term is given a definition, as original
Then, it need to be explained with the meaning and concept for meeting the technology of the present invention thought.
The positive active material for lithium secondary battery of the present invention includes the lithium nickel-manganese-cobalt oxidation represented with following chemical formula 1
Thing,
Chemical formula 1：
LiaNixMnyCozO2,
In above-mentioned chemical formula 1,1≤a≤1.2, x=1-y-z, 0 ＜ y ＜ 1,0 ＜ z ＜ 1, x ＞ y, z=ny or y=nz,
N ＞ 1.
Lithium nickel-manganese-cobalt/cobalt oxide that the positive active material for lithium secondary battery of the present invention is included meets x ＞ y pass
System.I.e., in one embodiment of this invention, above-mentioned lithium nickel-manganese-cobalt/cobalt oxide can include more nickel compared with manganese (Mn)
(Ni), and can have compared with manganese and cobalt (Co) composition of nickel excessively.Specifically, the content (x) of above-mentioned nickel can have
There are the value of 0.4≤x≤0.95, the preferably value with 0.6≤x≤0.85, the more preferably value with 0.6≤x≤0.82.
Above-mentioned nickel content be more than 0.4 in the case of, high power capacity can be expected, below 0.95 in the case of, can
Prevent the problem of security is reduced.
In the case of the actual identical of the content of manganese and nickel in above-mentioned lithium nickel-manganese-cobalt/cobalt oxide, Mn4+Ion can be induced
Ni2+The formation of ion, if therefore the manganese content of relative nickel is reduced in above-mentioned lithium nickel-manganese-cobalt/cobalt oxide, Ni can be reduced2+From
The formation of son, the Ni being consequently formed2+Ion forms rock salt structure by being moved to reversible Li sites (site), so as to reduce
The possibility for making chemical property degenerate.
Therefore, lithium nickel-manganese-cobalt/cobalt oxide that the present invention above-mentioned positive active material of one is included, by with manganese
(Mn) compare comprising more nickel (Ni), the Ni in the transition metal that above-mentioned lithium nickel-manganese-cobalt/cobalt oxide is included can be reduced2+'s
Relative amount.
In above-mentioned lithium nickel-manganese-cobalt/cobalt oxide that the present invention above-mentioned positive active material of one is included, with above-mentioned manganese
The nickel of the corresponding amount of content can be with Ni2+Form is present, more than the nickel energy of the amount of content corresponding with the content of above-mentioned manganese
Enough with Ni3+Form is present.
Therefore, the nickel that above-mentioned positive active material is included can have the Average oxidation number bigger than+2, on the whole, upper
+ 3.0 can be exceeded by stating the Average oxidation number of the nickel in lithium nickel-manganese-cobalt/cobalt oxide in addition to above-mentioned lithium, manganese and cobalt.
Above-mentioned lithium nickel-manganese-cobalt/cobalt oxide includes：Transition metal-oxide skin(coating) (MO layers) comprising transition metal, and bag
Lithium-oxide skin(coating) (reversible lithium layer) containing lithium, in above-mentioned transition metal-oxide skin(coating) (MO layers), Ni2+And Ni3+Coexist, and
There can be above-mentioned Ni2+In a part be embedded in above-mentioned reversible lithium layer and with the above-mentioned MO layers form being combined.
On the other hand, above-mentioned Ni3+Size ratio have and Li+Similarly sized Ni2+It is small, therefore with above-mentioned Ni3+Increasing
Plus, transition metal-oxide skin(coating) (MO layers) comprising transition metal and lithium-oxide skin(coating) (reversible lithium layer) comprising lithium can be with bases
Suitably separated in the difference in size for the ion for occupying respective layer.That is, the transition in above-mentioned positive active material in addition to lithium
The Average oxidation number of metal is more than+3, therefore compared with situation of the Average oxidation number for+3, the overall size of transition metal ions
It can diminish, can become big with the difference in size of lithium ion therewith, so as to realize interlaminar separation well, therefore stabilization can be formed
Layered crystal structure.
With the Ni in whole Li sites2+The ratio meter of institute mass point, the Ni of embedded above-mentioned reversible lithium layer2+Content can be with
Below 5 molar percentages, below preferably 3 molar percentages, for example, can be 0.01 molar percentage to 5 Mole percents
Than, 0.01 molar percentage to 3 molar percentages, 0.1 molar percentage to 5 molar percentages or 0.1 molar percentage to 3 rub
Your percentage etc..In the Ni of embedded above-mentioned reversible lithium layer2+Content in the case of below 5 molar percentages, by making insertion
The Ni of reversible lithium layer2+To the minimum interference of occlusion and the release of lithium ion, excellent multiplying power property can be played.
On the other hand, now, on the basis of the gross weight of nickel ion, above-mentioned Ni2+Amount be 0.1 percentage by weight to 2 weights
Percentage is measured, is specifically as follows 0.5 percentage by weight to 1.5 percentage by weights.
As described above, in the case where more stably forming the layered crystal structure of above-mentioned positive active material, Ke Yizeng
Strong high power charging-discharging characteristic.
If the Average oxidation number of transition metal excessively becomes big, the quantity of electric charge that lithium ion is moved can be made to reduce, so that
The problem of capacity is reduced can be caused, therefore, the Average oxidation number of transition metal can be more than 3 and less than 3.5, preferably greater than 3
And less than 3.3, more preferably higher than 3 and less than 3.1.
On the other hand, for the composition of above-mentioned lithium nickel-manganese-cobalt/cobalt oxide, the content (a) of above-mentioned lithium meet 1≤a≤
1.2, in the case where above-mentioned a values are less than 1.2, suitable high temperature safety can be played, in the situation that above-mentioned a values are more than 1
Under, reversible capacity can not be reduced while suitable multiplying power property is played.
For the composition for lithium nickel-manganese-cobalt/cobalt oxide that the present invention positive active material of one is included, above-mentioned manganese
Content (y) and the content (z) of cobalt z=ny can be met, now, above-mentioned n can be n ＞ 1.Unlike this, above-mentioned n can be
Natural number in addition to 1, can be 2 to 5 natural number.That is, the cobalt content of above-mentioned lithium nickel-manganese-cobalt/cobalt oxide can be more than manganese,
The content of above-mentioned cobalt can be n times of the content of manganese.
Lithium nickel-manganese-cobalt/cobalt oxide that the positive active material of the present invention one is included, by making the above-mentioned cobalt included
Amount it is more than above-mentioned manganese, therefore relative increase electrical conductivity thus, it is possible to improve multiplying power property, and can realize positive-active
The high powder density of material.
On the other hand, the composition of the lithium nickel-manganese-cobalt/cobalt oxide included for positive active material of the invention another
For composition, the content (y) of above-mentioned manganese and the content (z) of cobalt can meet y=nz, and now, above-mentioned n can be n ＞ 1.With this not
Together, above-mentioned n can be the natural number in addition to 1, and can be 2 to 5 natural number.That is, above-mentioned lithium nickel-manganese-cobalt/cobalt oxide
The content of manganese can be more than cobalt, and the above-mentioned manganese included can be n times of the content of cobalt.
The amount of above-mentioned manganese in lithium nickel-manganese-cobalt/cobalt oxide that the positive active material of another example of the invention is included is than upper
State that cobalt is more, thus with lithium nickel-manganese-cobalt/cobalt oxide more than manganese of the cobalt that is included or the manganese and the content identical lithium of cobalt that are included
Nickel-manganese-cobalt/cobalt oxide is compared, comprising manganese content it is relatively many, therefore the Ni induced by the presence of above-mentioned manganese2+Content
Also it is relative to increase, it thus can play the increased effect of battery capacity.Also, manganese can be to the Stability Analysis of Structures of lithium nickel-manganese-cobalt/cobalt oxide
Change plays positive role and thus embodies the characteristic needed for the lithium secondary battery of suitable high power capacity, and can be reduced with relative
The mode of cobalt content reduces Co unstable in the charge state4+Influence and thus improve stability.
In the lithium transition-metal oxide of the present invention, nickel, manganese and cobalt as transition metal are being able to maintain that stratiform knot
Other metallic elements can be partly substituted by the range of crystal structure, for example, can be partly substituted by a small amount of within 5 molar percentages
Metallic element, cation element etc..
Also, the present invention provides the positive pole for including above-mentioned positive active material.
Above-mentioned positive pole can be prepared by commonly used preparation method well known in the art.For example, can be lived in positive pole
Property material in mixing and stirring solvent, and mix and stir binding agent, conductive material, dispersant as needed and prepare slurry
Afterwards, above-mentioned slurry is coated on the current-collector of metal material and be compressed, be dried to prepare positive pole afterwards.
The current-collector of above-mentioned metal material is as the high metal of electric conductivity, as long as it is used as the slurry of above-mentioned positive active material
Expect the metal that can easily bond, without reactivity in the voltage range of battery, then any metal can be used.It is used as positive pole collection
The nonrestrictive example of electrical equipment, can be paper tinsel for being prepared by aluminium, nickel or combinations thereof etc..
There are 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), acetone, two for forming the solvent of above-mentioned positive pole
The organic solvents such as methylacetamide or water etc., these solvents can be used in the independent or two or more mode of mixing.Consider
The applied thickness of slurry, prepare yield, if the usage amount of solvent can reach dissolving and disperse above-mentioned positive active material, it is viscous
Tie agent, the degree of conductive material.
As above-mentioned binding agent, Kynoar-hexafluoropropene co-polymer (PVDF-co-HEP) can be used, gather inclined
PVF (polyvinylidenefluoride), polyacrylonitrile (polyacrylonitrile), polymethyl methacrylate
(polymethylmethacrylate), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regeneration are fine
Tie up element, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, polyacrylic acid, ethylene propylene diene rubber (EPDM), sulfonation three
First EP rubbers, butadiene-styrene rubber (SBR), fluorubber, polyacrylic acid (poly acrylic acid) and using Li, Na or Ca etc.
Come the polymer of the hydrogen that replaces above-mentioned substance, or a variety of binder polymers such as a variety of copolymers.
As long as above-mentioned conductive material will not cause chemical change and conductive to battery, just it is not particularly limited, example
Such as, the graphite of native graphite or electrographite etc. can be used；Carbon black, acetylene black, Ketjen black, channel carbon black, furnace blacks, lamp
The black and hot carbon black such as black；The conducting fibre such as carbon fiber or metallic fiber；The electric conductivity pipe such as CNT；Fluorocarbon, aluminium,
The metal dusts such as nickel by powder；The electric conductivity whisker such as zinc oxide, potassium titanate；The conductive metal oxides such as titanium oxide；Polyhenylene spreads out
The conductive materials such as biology.
Above-mentioned dispersant can use the organic dispersing agents such as water class dispersant or 1-METHYLPYRROLIDONE.
Also, the present invention provides the lithium for including above-mentioned positive pole, negative pole and the barrier film between above-mentioned positive pole and negative pole
Secondary cell.
As the negative electrode active material for above-mentioned negative pole of one embodiment of the invention, can be used usually can absorb and
Discharge carbon material, lithium metal, silicon or tin of lithium ion etc..Carbon material is preferably used, as carbon material, low-crystalline carbon and high knot
Crystalline substance carbon etc. can be used.As low-crystalline carbon, representative has soft carbon (soft carbon) and hard carbon (soft
Carbon), as high crystalline carbon, representative has native graphite, kish (Kish graphite), pyrolytic carbon
(pyrolytic carbon), mesophase pitch-based carbon fibers (mesophase pitch based carbon fiber), in
Between phase carbon microspheres (meso-carbon microbeads), mesophase pitch (Mesophase pitches) and oil or coal tar
The high-temperature calcination carbon of oil asphalt Jiao (petroleum or coal tar pitch derived cokes) etc..
Also, anode collector is generally prepared with 3 μm to 500 μm of thickness.As long as this anode collector will not be to electricity
Pond causes chemical change and conductive, is just not particularly limited, for example, copper can be used, and stainless steel, aluminium, nickel, titanium, forges
Burn carbon, be surface-treated using carbon, nickel, titanium, silver etc. on the surface of copper or stainless steel, aluminium-cadmium alloy etc..Also, with just
Pole current-collector is identical, can form fine bumps on surface to strengthen the adhesion of negative electrode active material, and can with film, piece,
The variforms such as paper tinsel, net, porous plastid, foaming body, non-woven body are used.
Identical with positive pole, binding agent, conductive material for negative pole can be used the commonly used binding agent in the field, lead
Electric material.It can prepare after composition of cathode active materials, incite somebody to action mixing and stirring negative electrode active material and above-mentioned additive
Above-mentioned composition of cathode active materials is coated on current-collector and is compressed to prepare negative pole.
Also, as above-mentioned barrier film, the common porous for being used as barrier film in the past can be used individually or in the way of stacking
Polymer film, for example, utilizing Alathon, Noblen, ethylene/butylene copolymers, ethylene/hexene copolymer and second
The polyolefin macromoleculars such as alkene/methyl acrylate copolymer are come the porous polymer film for preparing, or can use common
Porous nonwoven cloth, for example, the non-woven fabrics being made up of dystectic glass fibre, pet fiber, but
It is not limited thereto.
In the present invention, as long as the lithium salts that can be included as electrolyte is that typically used in secondary cell electrolyte
, it is just unrestricted, for example, as the anion of above-mentioned lithium salts, can use selected from by F-、Cl-、Br-、I-、NO3 -、N
(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、
CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3
(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-And (CF3CF2SO2)2N-One kind in the group of composition.
Workable electrolyte has the organic liquid electrolyte that can be used when preparing lithium secondary battery, nothing in the present invention
Machine class I liquid I electrolyte, solid polymer electrolyte, gel-type polymer electrolyte, solid inorganic electrolytes, fusion are inorganic
Electrolyte etc., but be not limited thereto.
The profile of the lithium secondary battery of the present invention is simultaneously not particularly limited, and can have the cylindrical shape for using tank, square, bag
(pouch) shape or coin (coin) shape etc..
The battery unit that the lithium secondary battery of the present invention can not only be used in as the power supply of midget plant to use, and
And be preferably able to be used in the big-and-middle-sized battery module including multiple battery units as unit cells.
It is used as the preference of above-mentioned big-and-middle-sized device, although electric automobile, mixed power electric car, plug-in can be enumerated
Formula mixed power electric car and electric power storage system etc., but be not limited thereto.
For the form carried out an invention
Embodiment
Hereinafter, enumerate embodiment and experimental example to carry out in more detail specifically to further illustrate the present invention
It is bright, but the present invention do not limited by these embodiments and experimental example.It is to be understood that embodiments of the invention can be deformed
For a variety of different forms, the scope of the present invention should not be limited to following embodiments.Embodiments of the invention are used for this hair
Bright person of an ordinary skill in the technical field more completely illustrates the present invention.
Embodiment 1：Prepare lithium nickel-manganese-cobalt/cobalt oxide
So that Ni:Mn:Co mol ratio reaches 8.2:0.6:1.2 mode is to nickel sulfate (Ni-sulfate), manganese sulfate
(Mn-sulfate) and cobaltous sulfate (Co-sulfate) is weighed, and it is dissolved in water to prepare the aqueous solution, passes through coprecipitated mode afterwards
To obtain nickel-manganese-cobalt complex metal hydroxide.So that Li:The mol ratio of nickel-manganese-cobalt reaches 1:1 mode is in above-mentioned metal
Li is put into hydroxide2CO3, afterwards by carrying out the heat treatment of 20 hours at 800 DEG C of the electric furnace of oxygen atmosphere, so as to obtain
With LiNi0.82Co0.12Mn0.06O2Lithium nickel-manganese-cobalt/cobalt oxide of composition.
Embodiment 2：Prepare lithium nickel-manganese-cobalt/cobalt oxide
So that Ni:Mn:Co mol ratio reaches 8.2:1.2:0.6 mode is weighed to nickel sulfate, manganese sulfate and cobaltous sulfate,
And be dissolved in water to prepare the aqueous solution, nickel-manganese-cobalt complex metal hydroxide is obtained by coprecipitated mode afterwards.So that Li:
The mol ratio of nickel-manganese-cobalt turns into 1:1 mode is put into Li in above-mentioned metal hydroxides2CO3, pass through oxygen atmosphere afterwards
The heat treatment of progress 20 hours at 800 DEG C of electric furnace, so as to obtain with LiNi0.82Co0.06Mn0.12O2Lithium nickel-manganese-cobalt of composition
Oxide.
Embodiment 3：Prepare lithium nickel-manganese-cobalt/cobalt oxide
So that Ni:Mn:Co mol ratio reaches 7.6:0.6:1.8 mode is weighed to nickel sulfate, manganese sulfate and cobaltous sulfate,
And be dissolved in water to prepare the aqueous solution, nickel-manganese-cobalt complex metal hydroxide is obtained by coprecipitated mode afterwards.So that Li:
The mol ratio of nickel-manganese-cobalt reaches 1:1 mode is put into Li in above-mentioned metal hydroxides2CO3, pass through oxygen atmosphere afterwards
The heat treatment of progress 20 hours at 800 DEG C of electric furnace, so as to obtain with LiNi0.76Co0.18Mn0.06O2Lithium nickel-manganese-cobalt of composition
Oxide.
Embodiment 4：Prepare lithium nickel-manganese-cobalt/cobalt oxide
So that Ni:Mn:Co mol ratio reaches 5.2:1.2:3.6 mode is weighed to nickel sulfate, manganese sulfate and cobaltous sulfate,
And be dissolved in water to prepare the aqueous solution, nickel-manganese-cobalt complex metal hydroxide is obtained by coprecipitated mode afterwards.So that Li:
The mol ratio of nickel-manganese-cobalt reaches 1:1 mode is put into Li in above-mentioned metal hydroxides2CO3, pass through oxygen atmosphere afterwards
The heat treatment of progress 20 hours at 800 DEG C of electric furnace, so as to obtain with LiNi0.52Co0.36Mn0.12O2Lithium nickel-manganese-cobalt of composition
Oxide.
Comparative example 1：Prepare lithium nickel-manganese-cobalt/cobalt oxide
Except nickel sulfate, manganese sulfate and cobaltous sulfate are reached into 8 with mol ratio in above-described embodiment 1:1:1 mode claims
Measure outside use, obtain has LiNi in the same manner as in Example 10.8Co0.1Mn0.1O2Lithium nickel-manganese-cobalt oxidation of composition
Thing.
Comparative example 2：Prepare lithium nickel-manganese-cobalt/cobalt oxide
Except nickel sulfate, manganese sulfate and cobaltous sulfate are reached into 8.5 with mol ratio in above-described embodiment 1:0.6:0.9 side
Formula is weighed outside use, and obtain has LiNi in the same manner as in Example 10.85Co0.09Mn0.06O2The lithium nickel of composition-
Manganese-cobalt/cobalt oxide.
Comparative example 3：Prepare lithium nickel-manganese-cobalt/cobalt oxide
Except nickel sulfate, manganese sulfate and cobaltous sulfate are reached into 8.5 with mol ratio in above-described embodiment 1:0.7:0.8 side
Formula is weighed outside use, and obtain has LiNi in the same manner as in Example 10.85Co0.08Mn0.067O2The lithium nickel of composition-
Manganese-cobalt/cobalt oxide.
Embodiment 5：Prepare lithium secondary battery
<The preparation of positive pole>
The institute in above-described embodiment 1 of 94 percentage by weights is added to the METHYLPYRROLIDONE (NMP) as solvent
Lithium nickel-manganese-cobalt/cobalt oxide of preparation, the carbon black (carbon black) as conductive material of 3 percentage by weights, 3 weight hundred
Divide the Kynoar (PVdF) as binding agent of ratio, to prepare cathode mix slurry.It it is 20 μm or so in thickness
As applying the above-mentioned cathode mix slurry of preparation on aluminium (Al) film of cathode collector, and it is dried to prepare just
Pole, implements roll-in (roll press) to prepare positive pole afterwards.
<The preparation of negative pole>
The conduct for mixing the carbon dust, 1.0 percentage by weights as negative electrode active material of 96.3 percentage by weights is conductive
The conductive carbon black (super-p) of material, the butadiene-styrene rubber (SBR) as binding agent of 1.5 percentage by weights and 1.2 weight percents
The carboxymethyl cellulose (CMC) as binding agent of ratio, and added to as in the NMP of solvent, so as to prepare negative electrode active
Compound paste.It is the above-mentioned negative electrode active material prepared by being applied on 10 μm copper (Cu) film as anode collector in thickness
Chylema material, and be dried to prepare negative pole, implement roll-in afterwards to prepare negative pole.
<The preparation of nonaqueous electrolyte>
With 30:It is non-aqueous that 70 volume ratio mixing is prepared as the ethylene carbonate and diethyl carbonate of electrolyte
LiPF is added in electrolyte solvent6, prepare 1M LiPF6Nonaqueous electrolyte.
<The preparation of lithium secondary battery>
Make the barrier film of mix polyethylene and polypropylene after the positive pole and negative pole prepared according to the above method,
Polymer-type cell is made using usual way, the above-mentioned nonaqueous electrolyte prepared according to the above method is injected afterwards, comes
Prepare lithium secondary battery.
Embodiment 6 to 8：Prepare lithium secondary battery
Above-described embodiment 5 positive pole prepare in except as lithium nickel-manganese-cobalt/cobalt oxide replace embodiment 1 in lithium nickel-
Manganese-cobalt/cobalt oxide and use respectively outside lithium nickel-manganese-cobalt/cobalt oxide that embodiment 2 is prepared into embodiment 4, with implementation
The identical method of example 5 prepares positive pole, and with preparing negative pole in the method identical method described in embodiment 5 and non-
Aqueous electrolyte, then prepares lithium secondary using the positive pole, negative pole and nonaqueous electrolyte that prepare in the manner
Battery.
Comparative example 4 to 6：Prepare lithium secondary battery
In addition to using respectively in the above-mentioned comparative example 1 lithium nickel-manganese-cobalt/cobalt oxide prepared into comparative example 3, with
The identical method of embodiment 5 prepares lithium secondary battery.
Experimental example 1：SEM microphotographs
Using electron microscope (SEM) with different multiplying shoot the lithium nickel-manganese prepared in above-described embodiment and comparative example 1-
The photo of cobalt/cobalt oxide, and its result is shown in Fig. 1 and Fig. 2.
Experimental example 2：Determine crystalline texture
Using the X- lines diffraction (XRD, Rigaku, D/MAX-2500 (18kW)) radiated using CuK α, above-mentioned implementation is determined
The crystalline texture for lithium nickel-manganese-cobalt/cobalt oxide that example 1 to embodiment 4, comparative example 1 is prepared into comparative example 3.What is determined is above-mentioned
The lattice of the a- and c- axles for lithium nickel-manganese-cobalt/cobalt oxide that embodiment 1 to embodiment 4, comparative example 1 is prepared into comparative example 3 is normal
Number, crystallite size, crystal density and Ni2+Ratio shown respectively in table 1.Above-mentioned Ni2+Ratio represent with the total of Ni ions
Ni on the basis of weight2+Weight.
Table 1
With reference to above-mentioned table 1, it can confirm that embodiment 1 is embedded in the situation of embodiment 4 compared with comparative example 1 to comparative example 3
The Ni in lithium site2+Ratio it is less.
Experimental example 3：Cycle characteristics evaluation experimental
It is based in order to which the lithium secondary battery respectively obtained to embodiment 5 to embodiment 8, comparative example 4 into comparative example 6 understands
The relative efficiency of period, performs following electrochemical evaluation experiment.
Specifically, to the lithium secondary battery that is prepared respectively in embodiment 5 and comparative example 4 at 45 DEG C with the constant of 1C
Untill electric current (CC) charges to 4.20V, then charged with 4.20V constant voltage (CV), until charging current turns into
0.05mAh, thus implements to charge for the first time.Place afterwards 20 minutes, 2.5V is then discharged to 2C constant current progress and (cut
Only (cut-off) is carried out with 0.05C) untill.Implement 1 time to 100 times circulation repeatedly to this.Its result is as shown in Figure 3.
Fig. 3 is the chart of the life characteristic for the lithium secondary battery for showing embodiment 5 and comparative example 4, can be confirmed by Fig. 3,
In the lithium secondary battery of embodiment 5, the gradient and the lithium of comparative example 4 of the relative capacity untill 1 time to 100 times circulation are secondary
Battery is compared to more gentle, for the increase gradient of resistance, can confirm the lithium secondary battery and comparative example 4 of embodiment 5
Lithium secondary battery compared to also gentler.
That is, the content identical of the lithium secondary battery and manganese and cobalt of the embodiment 5 less than cobalt of manganese used in can confirming
The lithium secondary battery of comparative example 4 is compared, and life characteristic is more excellent.
Also, the lithium secondary battery prepared respectively into comparative example 6 in embodiment 6 to embodiment 8, comparative example 4 is at 45 DEG C
Under untill 0.5C constant current (CC) charges to 4.25V, then charged with 4.25V constant voltage (CV), until charging
Electric current turns into 0.05mAh, thus implements to charge for the first time.Place 20 minutes, be then discharged to 1C constant current afterwards
Untill 3.0V (cut-off is carried out with 0.05C).Implement 1 time to 50 times circulation repeatedly to this.The results are shown in Fig. 4.
It can be confirmed by Fig. 4, in the lithium secondary battery of embodiment 6 to embodiment 8, the phase untill 1 time to 40 times circulation
To the gradient of capacity compared with the lithium secondary battery of comparative example 4 to comparative example 6 it is gentler.
Therefore, as shown in the embodiment of the present invention, when being n times of cobalt by the content of cobalt is manganese n times or the content of manganese
The Ni in embedded Li sites2+The less lithium nickel-manganese-cobalt/cobalt oxide of ratio be used as positive active material in the case of, can be to two
The circulation degeneration of primary cell is relaxed, and shows the cycle characteristics of long-time stable.
Experimental example 4：Utilize the measure of the resistance of HPPC lithium secondary battery
To perform HPPC (hybrid pulse power characterization, hybrid power pulse ability characteristics)
The mode of experiment is measured come the resistance to lithium secondary battery prepared in above-described embodiment 5 and comparative example 4.With 1C
(30mA) is charged untill 4.15V, from SOC (charged state) 10 untill fully charged (SOC=100), and to battery
The stabilisation of 1 hour is carried out respectively, then according to the resistance of HPPC determination of experimental method lithium secondary batteries, on the other hand, from SOC
Battery is discharged untill 100 to 10, and after carrying out the stabilisation of 1 hour respectively to battery, the base in each SOC stages
Go out the resistance of lithium secondary battery in HPPC determination of experimental method.Resistance value during discharge and recharge is as shown in Figure 5.
Can be confirmed by Fig. 5, for all charging resistor and discharge resistance, using embodiment 1 lithium nickel-manganese-
The lithium secondary battery of cobalt/cobalt oxide is shown more compared with using the lithium secondary battery of the lithium of comparative example 1 nickel-manganese-cobalt/cobalt oxide
Low value, can show height output.
Claims (13)
1. a kind of positive active material for lithium secondary battery, it is characterised in that comprising the lithium nickel-manganese represented with following chemical formula 1-
Cobalt/cobalt oxide,
Chemical formula 1：
LiaNixMnyCozO2,
In the chemical formula 1,1≤a≤1.2, x=1-y-z, 0 ＜ y ＜ 1,0 ＜ z ＜ 1, x ＞ y, z=ny or y=nz, n
＞ 1.
2. positive active material for lithium secondary battery according to claim 1, it is characterised in that the x has 0.4≤x
≤ 0.95 value.
3. positive active material for lithium secondary battery according to claim 1, it is characterised in that in the lithium nickel-manganese-cobalt
In the nickel that oxide is included, the nickel of the amount corresponding with the content of the manganese is with Ni2+Form is present.
4. positive active material for lithium secondary battery according to claim 3, it is characterised in that in the lithium nickel-manganese-cobalt
In the nickel that oxide is included, more than the content corresponding with the content of the manganese amount nickel with Ni3+Form is present.
5. positive active material for lithium secondary battery according to claim 1, it is characterised in that the Ni has bigger than+2
Average oxidation number.
6. positive active material for lithium secondary battery according to claim 1, it is characterised in that in addition to the Li
Ni, Mn and Co Average oxidation number are more than 3.0.
7. positive active material for lithium secondary battery according to claim 1, it is characterised in that the lithium nickel-manganese-cobalt oxide
Compound includes：
Transition metal-oxide skin(coating) comprising transition metal is MO layers, and
Lithium-oxide skin(coating) comprising lithium is reversible lithium layer,
Described MO layers includes Ni2+And Ni3+,
The Ni2+In a part be embedded in reversible lithium layer.
8. positive active material for lithium secondary battery according to claim 7, it is characterised in that as in reversible lithium layer institute
Comprising whole Li sites in Ni2+The ratio of institute mass point, the Ni of the embedded reversible lithium layer2+Content be 5 Mole percents
Than following.
9. positive active material for lithium secondary battery according to claim 7, it is characterised in that with the gross weight of nickel ion
As benchmark, the Ni2+Weight be 0.1 percentage by weight to 2 percentage by weights.
10. positive active material for lithium secondary battery according to claim 1, it is characterised in that the n is oneself of 2 to 5
So count.
11. a kind of positive electrode for lithium secondary battery, it is characterised in that include the lithium two described in any one of claim 1 to 10
Primary cell positive active material.
12. a kind of lithium secondary battery, it is characterised in that including the positive electrode for lithium secondary battery described in claim 11.
13. lithium secondary battery according to claim 12, it is characterised in that the lithium secondary battery be used for electric automobile,
The power supply of mixed power electric car or plug-in hybrid electric automobile.
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| KR20150028378 | 2015-02-27 | ||
| KR10-2015-0028378 | 2015-02-27 | ||
| PCT/KR2016/001957 WO2016137287A1 (en) | 2015-02-27 | 2016-02-26 | Cathode active material, cathode comprising same, and lithium secondary battery |
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| CN114982008A (en) * | 2019-12-26 | 2022-08-30 | 汉阳大学校产学协力团 | Fluorine-containing positive electrode active material for lithium secondary battery and lithium secondary battery comprising same |
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| WO2024085629A1 (en) * | 2022-10-18 | 2024-04-25 | 주식회사 엘지에너지솔루션 | Positive electrode and lithium secondary battery including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102150305A (en) * | 2008-09-10 | 2011-08-10 | 株式会社Lg化学 | Cathode active material for lithium secondary battery |
| CN102439765A (en) * | 2009-02-13 | 2012-05-02 | 株式会社Lg化学 | Lithium secondary battery with improved energy density |
| CN102983322A (en) * | 2006-05-10 | 2013-03-20 | 株式会社Lg化学 | Material for lithium secondary battery of high performance |
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| JP3798923B2 (en) * | 1999-07-23 | 2006-07-19 | セイミケミカル株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| JP4713886B2 (en) * | 2002-12-06 | 2011-06-29 | 株式会社東芝 | Nonaqueous electrolyte secondary battery |
| KR101171734B1 (en) * | 2009-04-01 | 2012-08-07 | 주식회사 엘지화학 | Cathode Active Material for Lithium Secondary Battery |
| KR101689214B1 (en) * | 2011-10-28 | 2016-12-26 | 삼성에스디아이 주식회사 | Nickel composite hydroxide for lithium secondary battery, lithium complex oxide for lithium secondary battery prepared therefrom, preparing method thereof, positive electrode including the same, and lithium secondary battery employing the same |
| KR101496511B1 (en) * | 2012-02-08 | 2015-02-27 | 주식회사 엘지화학 | Lithium secondary battery |
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2016
- 2016-02-26 WO PCT/KR2016/001957 patent/WO2016137287A1/en active Application Filing
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| CN102983322A (en) * | 2006-05-10 | 2013-03-20 | 株式会社Lg化学 | Material for lithium secondary battery of high performance |
| CN102150305A (en) * | 2008-09-10 | 2011-08-10 | 株式会社Lg化学 | Cathode active material for lithium secondary battery |
| CN102439765A (en) * | 2009-02-13 | 2012-05-02 | 株式会社Lg化学 | Lithium secondary battery with improved energy density |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114982008A (en) * | 2019-12-26 | 2022-08-30 | 汉阳大学校产学协力团 | Fluorine-containing positive electrode active material for lithium secondary battery and lithium secondary battery comprising same |
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