CN101140987A - Lithium manganese oxide and manufacturing method thereof, lithium secondary cell and positive active materials - Google Patents
Lithium manganese oxide and manufacturing method thereof, lithium secondary cell and positive active materials Download PDFInfo
- Publication number
- CN101140987A CN101140987A CNA2007101498245A CN200710149824A CN101140987A CN 101140987 A CN101140987 A CN 101140987A CN A2007101498245 A CNA2007101498245 A CN A2007101498245A CN 200710149824 A CN200710149824 A CN 200710149824A CN 101140987 A CN101140987 A CN 101140987A
- Authority
- CN
- China
- Prior art keywords
- limn2o4
- secondary battery
- lithium secondary
- lithium
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a lithium secondary battery anode auxiliary active compound which is difficult in drop of discharge capacity during common use and is capable of reducing performance deterioration caused by over discharge. The lithium secondary battery anode auxiliary active compound adopts a lithium manganate which is characterized in that the lithium manganate can be represented by the general formula (1) of LixMnO2, wherein 0.90<=x<=1.05, and in Lab, the values of L, a and b are respectively 25.0-32.0, -1.50-0.15 and 2.50-8.00.
Description
Technical field
The present invention relates to can be as the LiMn2O4 and the LiMn2O4 manufacture method that can use in the manufacturing of this LiMn2O4 of the anodal secondary active material of lithium secondary battery, contain cathode active material for lithium secondary battery and the lithium secondary battery of this LiMn2O4 as the secondary active material of positive pole.
Background technology
In recent years, along with developing rapidly of the portability of household electrical appliance, wireless penetration, lithium rechargeable battery is as the power supply of compact electronic devices such as pocket pc, mobile phone, video camera and be practical.About this lithium rechargeable battery, since water island etc. is useful (" テ リ ァ Le リ サ one チ Block レ テ ィ Application " vol15 at 1980 annual report cobalts acid lithium as the positive active material of lithium rechargeable battery, p783-789 (1980)) since, research and development about the lithium system complex oxide make progress actively, form many motions so far.
But with the lithium secondary battery of lithium system complex oxide as positive active material, as Copper Foil stripping in electrolyte when over-discharge can of negative electrode collector, and its part separates out at positive pole, and just there is the problem of the easy deterioration of charge-discharge characteristic in the result.Therefore, adopt the circuit that prevents over-discharge can in the battery arranged outside, preventing the method for over-discharge can, but owing to prevent the circuit of over-discharge can and exist, use the cost of the device of battery or battery pack etc. to uprise.
The positive active material of above-mentioned lithium secondary battery contains the lithium system complex oxide as main active material, and does not contain secondary active material.On the other hand, propose with LiCoO
2Deng the lithium system complex oxide is main active material, to wherein adding LiMnO
2The method of using as secondary active material promptly, contains the LiCoO as main active material
2Deng the lithium system complex oxide with as the LiMnO of secondary active material
2Cathode active material for lithium secondary battery.For example, in the Japanese patent laid-open 6-349493 of patent documentation 1 communique, disclose and contained LiCoO
2Deng being mixed with LiMnO in the lithium-contained composite oxide
2The nonaqueous electrolytic solution secondary battery made as positive active material of material.The LiMnO that in this patent documentation 1, uses
2, be in inactive gas atmosphere, to fire MnO
2Make with lithium carbonate, at the LiMnO that will in this patent documentation 1, obtain
2As in the lithium secondary battery of anodal secondary active material,, be easy to generate in using usually degradation problem under the discharge capacity though get to a certain degree improvement about the problem of over-discharge can.Therefore, wish a kind of secondary active material of cathode plate for lithium secondary battery that can give the battery performance of lithium secondary battery excellence of exploitation.
In addition, open in the 2002-151079 communique, disclose heat treated MnO the Japan Patent spy of patent documentation 2
2And the Mn that obtains
2O
3The LiMnO that fires with the mixture of lithium compound and obtain
2, with this LiMnO
2As the lithium secondary battery of positive active material, still, even with the LiMnO of this patent documentation 2
2As positive active material,, remain inadequate as degradation way to solve the problem under the problem of over-discharge can and the discharge capacity.
In addition, the application's applicant etc. open in the 2006-139945 communique the Japan Patent spy that the Japan Patent spy of patent documentation 3 opens 2005-235416 communique or patent documentation 4, propose can be used in the LiMn2O4 of the secondary active material of cathode plate for lithium secondary battery.Adopt the secondary active material of cathode plate for lithium secondary battery of patent documentation 3 or patent documentation 4 can improve degradation problem under the problem of over-discharge can and the discharge capacity to a certain extent, seeking further improvement.
Patent documentation 1: Japanese patent laid-open 6-349493 communique (claims)
Patent documentation 2: the Japan Patent spy opens 2002-151079 communique (claims, embodiment 2)
Patent documentation 3: the Japan Patent spy opens 2005-235416 communique (claims)
Patent documentation 4: the Japan Patent spy opens 2006-139945 communique (claims)
Summary of the invention
Therefore, it is a kind of in using usually that problem of the present invention is to provide, discharge capacity descends difficult, and the cathode plate for lithium secondary battery that can reduce the performance degradation that causes because of over-discharge can secondary active material, its manufacture method, use the cathode active material for lithium secondary battery of the secondary active material of this cathode plate for lithium secondary battery, and provide a kind of in using usually, discharge capacity descends difficult, and the few lithium secondary battery of the performance degradation that causes because of over-discharge can.
The present inventor etc. have carried out deep repeatedly research in order to solve the problem that exists in above-mentioned prior art, found that to have at L
*a
*b
*The LiMn2O4 of the color of particular range in the colour system, as the secondary active material of positive pole, can be with the battery performance of excellence, particularly, capacity decline difficulty and over-discharge can in using usually can be suppressed the battery performance of effect excellence and give lithium secondary battery, thereby finish the present invention.
That is, the present invention (1) provides a kind of cathode plate for lithium secondary battery secondary active material LiMn2O4, it is characterized in that, with following general formula (1) expression, at L
*a
*b
*L in the colour system
*Value is 25.0～32.0, a
*Be-1.50～-0.15, b
*Be 2.50～8.00.
Li
xMnO
2 (1)
(in the formula, 0.90≤x≤1.05)
In addition, the present invention (2) provides a kind of manufacture method of LiMn2O4, it is characterized in that, comprising: in the inactive gas atmosphere below oxygen concentration is 1 volume %, fire non-alkaline carbonic acid manganese with 500～800 ℃, obtain first operation of MnO; In the atmosphere more than oxygen concentration is 10 volume %, fire with 525～950 ℃ and to carry out the MnO that this first operation obtains, obtain Mn
2O
3Second operation; With the mode that with mol ratio is 0.90～1.05, mix and carry out the Mn that this second operation obtains with respect to the lithium atom of manganese atom
2O
3With lithium compound, obtain reacting material mixture, then in the inactive gas atmosphere below oxygen concentration is 1 volume %, fire this reacting material mixture with 600～950 ℃, obtain the 3rd operation of LiMn2O4.
In addition, the present invention (3) provides a kind of cathode active material for lithium secondary battery, it is characterized in that, contains the lithium composite xoide that the secondary active material of cathode plate for lithium secondary battery of the invention described above (1) record use LiMn2O4 and represented with following general formula (2).
Li
(a)M
(1-b)A
(b)O
(c) (2)
(in the formula, M represents to be selected from the metallic element more than a kind of Co and Ni, and A represents to be selected from the metallic element more than a kind of Mg, Al, Ti, Zr, Fe, Cu, Zn, Sn, In, Ca, Ba, Sr and Mn, 0.9≤a≤1.1,0≤b≤0.5,1.8≤c≤2.2.)
In addition, the present invention (4) provides a kind of lithium secondary battery, it is characterized in that, the cathode active material for lithium secondary battery of record in the invention described above (3) can be obtained as positive active material.
According to the present invention, can provide a kind of in usually using the discharge capacity difficulty that descends, and can suppress to cause the secondary active material of cathode plate for lithium secondary battery, its manufacture method of performance degradation because of over-discharge can, with the cathode active material for lithium secondary battery that uses the secondary active material of this cathode plate for lithium secondary battery, in addition, can provide a kind of in usually using the discharge capacity difficulty that descends, and cause the lithium secondary battery that performance degradation is few because of over-discharge can.
Embodiment
LiMn2O4 of the present invention is with above-mentioned general formula (1) expression, at L
*a
*b
*L in the colour system
*Value is 25.0～32.0, a
*For-1.50～-0.15, b
*It is the secondary active material LiMn2O4 of 2.50～8.00 cathode plate for lithium secondary battery.That is, LiMn2O4 of the present invention is the LiMn2O4 as the secondary active material of the cathode plate for lithium secondary battery that constitutes cathode active material for lithium secondary battery.
In above-mentioned general formula (1), the value of x is 0.90≤x≤1.05, is preferably 0.95≤x≤1.01.Value by x is in above-mentioned scope, and the Li supply capacity of LiMn2O4 uprises.
LiMn2O4 of the present invention in X-ray diffraction is analyzed, is single-phase LiMn2O4.
Like this, the object color of LiMn2O4 of the present invention is different from the LiMn2O4 shown in the above-mentioned general formula (1), in the past always as the LiMn2O4 of the secondary active material of cathode plate for lithium secondary battery (below, to in the LiMn2O4 shown in the above-mentioned general formula (1), also note the LiMn2O4 of doing in the past by abridging as the LiMn2O4 of the secondary active material of cathode plate for lithium secondary battery) in the past always.That is, at the L of LiMn2O4 of the present invention
*a
*b
*L in the colour system
*Value is 25.0～32.0, is preferably 26.0～31.0, a
*Value is preferably-1.00～-0.10, b for-1.50～-0.15
*Value is 2.50～8.00, is preferably 3.50～7.00.The L of LiMn2O4 of the present invention
*a
*b
*L in the colour system
*Value, a
*Value and b
*Value can be given the battery performance of lithium secondary battery excellence thus in above-mentioned scope, therefore, can access discharge capacity decline difficulty, and the few lithium secondary battery of the performance degradation that causes because of over-discharge can.On the other hand, LiMn2O4 in the past is at L
*a
*b
*L in the colour system
*Value is about 15～40, a
*Value is about-10～-5, b
*Value is about 11～18.In addition, in the present invention, L
*a
*b
*L in the colour system
*Value, a
*Value and b
*Value is the aberration of being measured by colour difference meter, makes stipulations in JIS JIS Z 8730.
L
*a
*b
*L in the colour system
*Value representation brightness is worth big more whitely more, bleaches fully at 100 o'clock, be worth more little black more, complete blackening in 0 o'clock.In addition, a value and b value representation tone, a value is big more, and redness is dense more, and a value is more little, and green is dense more; The b value is big more, and yellow is dense more, and the b value is more little, and blueness is dense more.
LiMn2O4 of the present invention is a powder, color difference measurement as powder, can enumerate the method for the method of powder sample slurryization, pelletization, be filled in the special-purpose glassware with cover and carry out method for measuring etc., LiMn2O4 of the present invention is preferably to be filled in and carries out method for measuring in the glassware with cover.This be because, if adopt method with the LiMn2O4 slurryization, then in slurry,, Li changes because of breaking away to wait to take place to form, cause change color, thereby undesirable, in addition, if adopt the method for pelletization, then cause that because of reflection and pressurization etc. color changes at particle surface, thus undesirable.
Can be coated with battery lead plate equably from becoming, and the viewpoint that can suppress degradation of cell performance of being caused by current concentration etc. etc. sets out, the average grain diameter of LiMn2O4 of the present invention is preferably 1～25 μ m, is preferably 4～15 μ m especially.In addition, in the present invention, average grain diameter is the value of obtaining by laser method particle size distribution method.
The performance degradation of the lithium secondary battery that causes from the stripping that suppresses because of Mn perhaps can set out with the viewpoint that high efficiency is supplied with Li, and the BET specific area of LiMn2O4 of the present invention is preferably 0.2～2.0m
2/ g is preferably 0.4～1.0m especially
2/ g.
Gas produces and the viewpoint of the gelation of cathode mixture coating from suppressing, and the dispersion liquid pH when LiMn2O4 of the present invention is disperseed in water is preferably below 12, is preferably below 11.5 especially.In addition, the lower limit of the dispersion liquid pH when LiMn2O4 of the present invention is disperseed in water, because LiMn2O4 of the present invention itself is weakly alkaline, so pH is preferably 9.5.In addition, in the present invention, the pH when what is called is disperseed LiMn2O4 in water, expression adds 5g LiMn2O4 sample in the pure water of 100g, after 5 minutes, left standstill 5 minutes the value of the pH of supernatant after leaving standstill with pH meter mensuration again 25 ℃ of stirrings.
LiMn2O4 of the present invention contains in cathode active material for lithium secondary battery, in other words, also use with the lithium secondary battery main active substances as the secondary active material of cathode plate for lithium secondary battery, can generate the battery performance excellence thus, promptly, in usually using, the discharge capacity difficulty that descends, and cause the lithium secondary battery that performance degradation is few because of over-discharge can.
LiMn2O4 of the present invention is with respect to Mn with the Li atom in the lithium compound
2O
3In the mol ratio (Li/Mn) of Mn atom be 0.90～1.05 mode, the Mn that will obtain firing MnO more than 525 ℃
2O
3Mix and the thing that is uniformly mixed with lithium compound, with 600～950 ℃ of LiMn2O4s of firing this mixture and obtaining, particularly carry out first operation～the 3rd operation that following LiMn2O4 manufacture method of the present invention relates to successively and the LiMn2O4 that obtains, because of the Li supply capacity big preferred.
The manufacture method of LiMn2O4 of the present invention comprises: in the inactive gas atmosphere below oxygen concentration is 1 volume %, fire non-alkaline carbonic acid manganese with 500～800 ℃, obtain first operation of MnO; In the atmosphere more than oxygen concentration is 10 volume %, fire with 525～950 ℃ and to carry out the MnO that this first operation obtains, obtain Mn
2O
3Second operation; Be that 0.90～1.05 mode is mixed and carried out the Mn that this second operation obtains with lithium atom with respect to the mol ratio (Li/Mn) of manganese atom
2O
3With lithium compound, obtain reacting material mixture, then in the inactive gas atmosphere below oxygen concentration is 1 volume %, fire this reacting material mixture with 600～950 ℃, obtain the 3rd operation of LiMn2O4.
First operation is to fire non-alkaline carbonic acid manganese, obtains the operation of MnO.
The so-called non-alkaline carbonic acid manganese that first operation relates to refers to adding 10g manganese carbonate in the 100g ultra-pure water, is 6.0～7.8 at the pH of the water of 25 ℃ of stirrings after 5 minutes, is preferably 6.5～7.6 manganese carbonate.Therefore, the non-alkaline carbonic acid manganese that relates to of first operation is different from the manganese carbonate that is commonly referred to as alkaline carbonic acid manganese.Under the situation of alkaline carbonic acid manganese, in the 100g ultra-pure water, add 10g alkaline carbonic acid manganese, be more than 8.0 at the pH of the water of 25 ℃ of stirrings after 5 minutes.
Non-alkaline carbonic acid manganese, modulate ammonium carbamate solution in industrial employing by ammoniacal liquor and carbon dioxide, make the method that manganese monoxide reacts therein and make the method that manganous salts such as the manganese sulfate that is dissolved in the water, manganese chloride and carbonic hydroammonium as the carbonic acid source reacts and make the manganous hydroxide of non-alkaline carbonic acid manganese (Mn (OH)
2) content few.Therefore, adding the non-alkaline carbonic acid manganese of 10g in the 100g ultra-pure water, is 6.0～7.8 at the pH of the water of 25 ℃ of stirrings after 5 minutes, preferably becomes 6.5～7.6.
On the other hand, alkaline carbonic acid manganese makes the method that manganous salts such as the manganese sulfate that is dissolved in the water, manganese chloride and sodium carbonate as the carbonic acid source reacts and makes the manganous hydroxide of alkaline carbonic acid manganese (Mn (OH) in industrial employing
2) content many.Therefore, adding 10g alkaline carbonic acid manganese in the 100g ultra-pure water, is more than 8.0 at the pH of the water of 25 ℃ of stirrings after 5 minutes.
Other each rerum natura of the non-alkaline carbonic acid manganese that first operation relates to etc. has no particular limits, the average grain diameter that is easy to get calmly is to set out in the aspect of the LiMn2O4 of 1～25 μ m, the average grain diameter of the non-alkaline carbonic acid manganese that first operation relates to is preferably 1～30 μ m, is preferably 5～20 μ m especially.
In first operation, in the inactive gas atmosphere below oxygen concentration is 1 volume %, preferably in being the inactive gas atmosphere of 0～0.5 volume %, oxygen concentration carries out firing of non-alkaline carbonic acid manganese.By in above-mentioned atmosphere, carrying out firing of non-alkaline carbonic acid manganese, can access fine and close MnO.On the other hand, if oxygen concentration, then can not obtain fine and close MnO greater than 1 volume %.As the inactive gas that first operation relates to, can enumerate nitrogen, helium, argon gas etc.In addition, in first operation, when carrying out the firing of non-alkaline carbonic acid manganese, the oxidation for anti-block causes can contain reducing gass such as hydrogen on a small quantity in atmosphere.
In first operation, the firing temperature of non-alkaline carbonic acid manganese is 500～800 ℃, is preferably 550～700 ℃.If 500 ℃ of the firing temperature deficiencies of non-alkaline carbonic acid manganese then can not obtain MnO, and if surpass 800 ℃, aggegation grow then, the fillibility of LiMn2O4 descends.
In first operation, the firing time of non-alkaline carbonic acid manganese has no particular limits, and is preferably 1～20 hour, is preferably 5～15 hours especially.If the firing time deficiency of non-alkaline carbonic acid manganese 1 hour is then insufficient easily to the conversion of MnO, on the other hand,, on the quality of MnO, can not see big difference even carry out firing more than 20 hours, therefore inefficent easily.
The MnO that carries out first operation and obtain, the MnO that obtains than firing other manganese salt and fire condition and the MnO that obtains with other, impurity content is few.
Second operation is to fire to carry out the MnO that first operation obtains, and obtains Mn
2O
3Operation.
In second operation, in the atmosphere more than oxygen concentration is 10 volume %, preferably in the atmosphere more than oxygen concentration is 15 volume %, be to fire carrying out the MnO that first operation obtains in the atmosphere more than the 20 volume % particularly preferably in oxygen concentration.By in above-mentioned atmosphere, firing, can access the few Mn of impurity to carrying out the MnO that first operation obtains
2O
3On the other hand, if oxygen concentration less than 10%, then owing to hypoxgia, so MnO is to Mn
2O
3Conversion insufficient, generate impurity easily.Usually, firing preferably of carrying out that MnO that first operation obtains carries out carried out in atmosphere or in the oxygen atmosphere.
In second operation, be 525～950 ℃ to carrying out the temperature that MnO that first operation obtains fires, be preferably 550～750 ℃.If to carrying out 525 ℃ of the temperature less thaies that MnO that first operation obtains fires, then in MnO to Mn
2O
3Conversion become insufficient, therefore, the discharge capacity of LiMn2O4 as the lithium secondary battery of anodal secondary active material descended, and if surpass 950 ℃, then take place by Mn
2O
3To Mn
3O
4Conversion, therefore the result can only obtain the low LiMn2O4 of Li supply capacity, as the performance step-down of anodal secondary active material.In addition, if to carrying out temperature that MnO that first operation obtains fires above 750 ℃, then LiMn2O4 is being used as in the lithium secondary battery of anodal secondary active material, the voltage (charging voltage) that Li breaks away from has the tendency that uprises, therefore, be preferably 550～750 ℃ to carrying out the temperature that MnO that first operation obtains fires.
In second operation, have no particular limits carrying out the time that MnO that first operation obtains fires, be preferably 1～20 hour, be preferably 5～15 hours especially.If to carrying out the time less than 1 hour that MnO that first operation obtains fires, then to Mn
2O
3Conversion insufficient easily, on the other hand,, on the quality of MnO, can not see big difference even carry out firing more than 20 hours, therefore inefficent easily.
The 3rd operation is to fire to carry out the Mn that second operation obtains
2O
3The reacting material mixture that mixes with lithium compound and obtain obtains the operation of LiMn2O4.
In the 3rd operation, at first mix and carry out the Mn that second operation obtains
2O
3With lithium compound.
As the lithium compound that the 3rd operation relates to, for example, can enumerate lithium carbonate, lithium hydroxide, lithium nitrate etc., lithium compound can be independent a kind or make up more than 2 kinds.In the lithium compound that the 3rd operation relates to, lithium carbonate does not have hygroscopy, and byproduct of reaction does not produce moisture, and the dispersion liquid pH value when disperseing LiMn2O4 in water diminishes, thereby preferably.Rerum natura of the lithium compound that the 3rd operation is related to etc. without limits, from carrying out the aspect of the mixing of reacting material mixture equably, the average grain diameter of the lithium compound that the 3rd operation relates to is preferably below the 20 μ m, is preferably 3～10 μ m especially.
Carry out the Mn that second operation obtains
2O
3The mixed proportion of the lithium compound that relates to the 3rd operation, the Li atom in the lithium compound that relates to the 3rd operation is with respect to carrying out the Mn that second operation obtains
2O
3In mol ratio (Li/Mn) meter of Mn atom, be 0.90～1.05, and from accessing the big LiMn2O4 aspect of Li supply capacity, both mixed proportions are preferably 0.95～1.01.On the other hand, carry out the Mn that second operation obtains
2O
3If the mixed proportion less than 0.90 of the lithium compound that relates to the 3rd operation, then unreacted Mn
2O
3Residual and become the reason of Mn stripping, perhaps the Li supply capacity of LiMn2O4 diminishes, and if surpass 1.05, then generate the LiMn2O4 that contains more Li, the pH of the dispersion liquid when therefore disperseing in water uprises, and becomes the reason that battery securities such as producing gas descends.
To carrying out the Mn that second operation obtains
2O
3Mixed method when mixing with lithium compound can be any method of dry type or wet type, and the aspect from easy to manufacture is preferably dry type.Under the situation that dry type is mixed, preferred use can be with the mixed uniformly blender of reacting material mixture etc.
Then, the Mn that second operation obtains is carried out in mixing
2O
3And lithium compound, obtain reacting material mixture.
In the 3rd operation, next, in the inactive gas atmosphere below oxygen concentration is 1 volume %, preferably in oxygen concentration is inactive gas atmosphere below the 1000ppm, particularly preferably in oxygen concentration is in the inactive gas atmosphere below the 100ppm, and reacting material mixture is fired.By in above-mentioned atmosphere, reacting material mixture being fired, can access the discharge capacity difficulty that descends, and the LiMn2O4 used of the few secondary active material of cathode plate for lithium secondary battery of the performance degradation that causes because of over-discharge can.On the other hand, if oxygen concentration surpasses 1 volume %, then owing to also generate LiMn
2O
4, Li
2NO
3Deng, therefore, the LiMn2O4 that obtains is as the performance step-down of the anodal secondary active material of lithium secondary battery.As the inactive gas that the 3rd operation relates to, can enumerate nitrogen, helium, argon gas etc.
In the 3rd operation, the firing temperature of reacting material mixture is 600～950 ℃, is preferably 700～850 ℃.If 600 ℃ of the firing temperature deficiencies of reacting material mixture then react insufficient, therefore can not obtain good LiMn2O4, and if, then obtain the low LiMn2O4 of Li supply capacity above 950 ℃.
In the 3rd operation, firing time of reacting material mixture is had no particular limits, be preferably 1～20 hour, be preferably 5～15 hours especially.If the firing time deficiency of reacting material mixture 1 hour, then reaction is insufficient easily, on the other hand, even carry out firing more than 20 hours, can not see big difference on the quality of LiMn2O4, and is therefore inefficent easily.
In addition, in the 3rd operation, can fire repeatedly as required, also can when firing repeatedly, fire with the temperature lower than above-mentioned baking temperature range.
In the 3rd operation, after firing, suitably thing is fired in cooling, pulverizes as required, obtains LiMn2O4.In addition, as required and the pulverizing of carrying out, in the 3rd operation, fire and to obtain LiMn2O4 be that the situation of block of fragile combination is inferior suitably carries out.
Carry out the LiMn2O4 that the 3rd operation obtains, average grain diameter is 1～25 μ m, is preferably 4～15 μ m, and the BET specific area is 0.2～2.0m
2/ g is preferably 0.4～1.0m
2/ g.In addition, carry out the lithium compound that the 3rd operation obtains, at L
*a
*b
*L in the colour system
*Value is 25.0～32.0, is preferably 26.0～31.0, a
*Value is preferably-1.00～-0.10, b for-1.50～-0.15
*Value is 2.50～8.00, is preferably 3.50～7.00.
By selecting various the creating conditions in the LiMn2O4 manufacture method of the present invention, the LiMn2O4 that can select to obtain is at L
*a
*b
*L in the colour system
*Value, a
*Value and b
*Value.Create conditions as this, can enumerate
(i) use non-alkaline carbonic acid manganese as the raw material of first operation,
(ii) be chosen in the atmosphere when firing in first operation oxygen concentration,
(iii) be chosen in firing temperature when firing in first operation,
(iv) be chosen in the atmosphere when firing in second operation oxygen concentration,
(v) be chosen in firing temperature when firing in second operation,
(vi) select lithium compound kind that the 3rd operation relates to or purity,
(vii) select the lithium atom/manganese atom in the reacting material mixture that the 3rd operation relates to mol ratio,
(viii) be chosen in the atmosphere when firing in the 3rd operation oxygen concentration,
(ix) be chosen in firing temperature when firing in the 3rd operation.
Cathode active material for lithium secondary battery of the present invention contains the lithium secondary positive active material of the lithium composite xoide shown in LiMn2O4 of the present invention and the following general formula (2).
Li
(a)M
(1-b)A
(b)O
(c) (2)
(in the formula, M represents to be selected from the metallic element more than a kind of Co and Ni, and A represents to be selected from the metallic element more than a kind among Mg, Al, Ti, Zr, Fe, Cu, Zn, Sn, In, Ca, Ba, Sr and the Mn, 0.9≤a≤1.1,0≤b≤0.5,1.8≤c≤2.2.) promptly, cathode active material for lithium secondary battery of the present invention contains LiMn2O4 of the present invention as secondary active material, contains the lithium composite xoide shown in the above-mentioned general formula (2) as main active substances.
The LiMn2O4 of the present invention that contains in cathode active material for lithium secondary battery of the present invention as previously mentioned, is with following general formula (1) expression,
Li
xMnO
2 (1)
(in the formula, 0.90≤x≤1.05 are preferably 0.95≤x≤1.01.)
At L
*a
*b
*L in the colour system
*Value is 25.0～32.0, is preferably 26.0～31.0, a
*Value is preferably-1.00～-0.10, b for-1.50～-0.15
*Value is 2.50～8.00, is preferably 3.50～7.00 the secondary active material LiMn2O4 of cathode plate for lithium secondary battery.The LiMn2O4 of the present invention that contains in cathode active material for lithium secondary battery of the present invention, average grain diameter are preferably 1～25 μ m, are preferably 4～15 μ m especially, and in addition, the BET specific area is preferably 0.2～2.0m
2/ g is preferably 0.4～1.0m especially
2/ g, in addition, the pH of the dispersion liquid when disperseing in water is preferably below 12, is preferably below 11.5 especially.
Lithium composite xoide shown in the above-mentioned general formula (2) has no particular limits, if carry out illustration, then can enumerate LiCoO
2, LiNiO
2, LiNi
0.8Co
0.2O
2, LiNi
0.8Co
0.1Mn
0.1O
2, LiNi
0.4Co
0.3Mn
0.3O
2Deng.These lithium composite xoides can be independent combinations more than a kind or 2 kinds.Wherein, LiCoO
2Be extensive use of industrial, and with the synergy height of the secondary active material of cathode plate for lithium secondary battery of the present invention with LiMn2O4, thereby preferred.
The rerum natura of the lithium composite xoide shown in the above-mentioned general formula (2) etc. has no particular limits, from split pole with can suppress to conduct electricity bad aspect, the average grain diameter of the lithium composite xoide shown in the above-mentioned general formula (2) is preferably 1～30 μ m, is preferably 3～25 μ m especially.In addition, from improving the aspect of battery thermal stability, the BET specific area of the lithium composite xoide shown in the above-mentioned general formula (2) is preferably 0.1～2.0m
2/ g is preferably 0.2～1.0m especially
2/ g.
In cathode active material for lithium secondary battery of the present invention, containing of lithium composite xoide (main active substances) shown in LiMn2O4 of the present invention (secondary active material) and the above-mentioned general formula (2) proportionally is, lithium composite xoide shown in the above-mentioned general formula (2) of relative 100 mass parts, LiMn2O4 of the present invention is preferably 5～30 mass parts, is preferably 10～20 mass parts especially.Containing of lithium composite xoide shown in the above-mentioned general formula (2) is proportional in above-mentioned scope, and the decline of the discharge capacity of lithium secondary battery is difficult thus, and the performance degradation that causes because of over-discharge can reduces.On the other hand, lithium composite xoide shown in the above-mentioned general formula (2) of relative 100 mass parts is if LiMn2O4 less than 5 mass parts of the present invention then increase easily because of the performance degradation that over-discharge can causes, if and above 30 mass parts, then the discharge capacity of battery diminishes easily.
Lithium composite xoide shown in LiMn2O4 of the present invention and the above-mentioned general formula (2) is mixed equably, make cathode active material for lithium secondary battery of the present invention.The mixed method of the lithium composite xoide shown in LiMn2O4 of the present invention and the above-mentioned general formula (2) has no particular limits, and in wet method or dry method, uses the plant equipment of powerful shear action to modulate.In wet method, use devices such as ball mill, dispersion mill, homogenizer, vibration mill, sand mill, pulverizing mill and machine,massing to mix.On the other hand, in dry method, use devices such as high-speed mixer (high speedmixer), high-speed mixer (super mixer), the spherical mixer (Turbo Spheremixer) of turbine, Henschel mixer, nauta mixer and ribbon blender to mix.In addition, mixed method is not limited to the method for using the illustration plant equipment.In addition, after the mixing, can carry out pulverization process with airslide disintegrating mill etc., carry out the granularity adjustment according to hope.
Lithium secondary battery of the present invention, be with cathode active material for lithium secondary battery of the present invention as positive active material and the lithium secondary battery that obtains, have positive pole, negative pole, spacer and contain the nonaqueous electrolyte of lithium salts.
The positive pole that lithium secondary battery of the present invention relates to for example, is coating and dry cathode mixture etc. and the positive pole that forms on positive electrode collector.
The cathode mixture that lithium secondary battery of the present invention relates to is made up of cathode active material for lithium secondary battery of the present invention, conductive agent, adhesive and the filler that adds as required etc.That is, lithium secondary battery of the present invention evenly is coated with as the LiMn2O4 of the present invention of positive active material and the mixture of the lithium composite xoide shown in the above-mentioned general formula (2) on positive pole.Therefore, the lithium secondary battery that the present invention relates to, part throttle characteristics descends difficult, and cycle characteristics descends difficult.
The positive electrode collector that relates to as lithium secondary battery of the present invention, so long as in the battery that constitutes, do not cause the electrical conductivity body of chemical change, then have no particular limits, for example, can enumerate stainless steel, nickel, aluminium, titanium, fire carbon, carried out the surface-treated material at aluminium or stainless steel surfaces with carbon, nickel, titanium, silver.These materials both can be that the oxidation processes thing that peroxidating is handled is carried out on the surface, also can be to form concavo-convex surface treatment thing by surface treatment on the collector body surface.In addition, as the form of positive electrode collector, for example, can enumerate the formed body of paper tinsel, film, sheet, net, perforation thing, lath body, porous plastid, foaming body, fiber-like, nonwoven fabrics etc.The thickness of the positive electrode collector that lithium secondary battery of the present invention relates to has no particular limits, and is preferably 1～500 μ m.
Conductive agent as lithium secondary battery of the present invention relates to so long as do not cause the electrically conductive material of chemical change in the battery that constitutes, then has no particular limits, and for example, can enumerate graphite such as native graphite, Delanium; Carbon black classes such as carbon black, acetylene carbon black, section's qin carbon black (ketjen black), channel carbon black, oven process carbon black, dim, pyrolytic carbon black; Conducting fibre such as carbon fiber, metallic fiber class; Metal dust classes such as fluorocarbons, aluminium, nickel powder; Conductivity such as zinc oxide, potassium titanate whisker class; Conductive metal oxides such as titanium oxide; Or conductive material such as polyphenyl (polyphenylene) derivative, as native graphite, for example, can enumerate flaky graphite, flaky graphite, amorphous graphite etc.These conductive agents can be independent a kind or make up more than 2 kinds.In the cathode mixture that lithium secondary battery of the present invention relates to, conductive agent contain proportional to be 1～50 quality %, to be preferably 2～30 quality %.
The adhesive that relates to as lithium secondary battery of the present invention, for example, can enumerate starch, Kynoar, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinylpyrrolidone, tetrafluoroethene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated epdm, styrene butadiene ribber, fluorubber, tetrafluoroethene-hexafluoroethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride pentafluor propylene copolymer, propylene-TFE copolymer, ethylene-chlorotrifluoro-ethylene copolymer, biasfluoroethylene-hexafluoropropylene-TFE copolymer, vinylidene-perfluoro methyl vinyl ether-TFE copolymer, ethylene-acrylic acid copolymer or its ionomer thing (Na
+Ion etc.), ethylene-methacrylic acid copolymer or its ionomer thing (Na
+Ion etc.), ethylene-methyl acrylate copolymer or its ionomer thing (Na
+Ion etc.), ethylene-methyl methacrylate methyl terpolymer or its ionomer thing (Na
+Ion etc.), polysaccharide, thermoplastic resin such as poly(ethylene oxide), have the polymer of caoutchouc elasticity etc., these can be independent a kind or make up more than 2 kinds and use.In addition, when use contained functional group's the compound of polysaccharide and so on and lithium reaction, for example preferably adding, the compound of NCO and so on made its functional group's inactivation.In the cathode mixture that lithium secondary battery of the present invention relates to, the cooperation ratio of adhesive is 1～50 quality %, is preferably 5～15 quality %.
The filler that lithium secondary battery of the present invention relates to is the material of the volumetric expansion that suppresses anodal etc., adds as required.As filler, so long as in the battery that constitutes, do not cause the fibrous material of chemical change, can both use, for example, can enumerate the olefin polymer of polypropylene, polyethylene etc.; Fiber such as glass, carbon.In the cathode mixture that lithium secondary battery of the present invention relates to, filer content is not particularly limited, and is preferably 0～30 quality %.
The negative pole that lithium secondary battery of the present invention relates to is coated with negative material on negative electrode collector, drying etc. and forming.
Negative electrode collector as lithium secondary battery of the present invention relates to so long as do not cause the electrical conductivity body of chemical change in the battery that constitutes, then has no particular limits, and can enumerate copper, copper alloy, nickel etc.Particularly copper or copper alloy, if when over-discharge can, anodal current potential becomes 3.5Vvs.Li/Li
+About, oxidation dissolution then takes place, but because the lithium ion that lithium secondary battery of the present invention is given is many, therefore when over-discharge can, anodal current potential is lower than 3.5Vvs.Li/Li when discharging and recharging
+Therefore, than in lithium secondary battery in the past, the fail safe when in negative pole, using copper or copper alloy, in lithium secondary battery of the present invention, the fail safe when using copper or copper alloy in negative pole is especially high.In addition, these materials can be that the oxidation processes thing that peroxidating is handled is carried out on the surface, also can be to form concavo-convex surface treatment thing by surface treatment on the collector body surface.In addition, the form of the negative electrode collector that relates to as lithium secondary battery of the present invention for example, can be enumerated the formed body of paper tinsel, film, sheet, net, perforation thing, lath body, porous plastid, foaming body, fiber-like, nonwoven fabrics etc.The thickness of the negative electrode collector that lithium secondary battery of the present invention relates to has no particular limits, and is preferably 1～500 μ m.
The negative material that relates to as lithium secondary battery of the present invention, have no particular limits, for example, can enumerate carbonaceous material, composite oxide of metal, lithium metal, lithium alloy, Si system alloy, tin series alloy, metal oxide, electroconductive polymer, chalcogen compound, Li-Co-Ni based material etc.The carbonaceous material that relates to as negative material, for example, can enumerate be difficult to graphited material with carbon element, graphite is material with carbon element etc.As the metal oxide that negative material relates to, for example, can enumerate Sn
(p)D
1 (1-p)D
2 (q)O
(r)(in the formula, D
1Expression is selected from the element more than a kind among Mn, Fe, Pb and the Ge, D
2Expression is selected from the element more than a kind in Al, B, P, Si, periodic table the 1st family, the 2nd family, the 3rd family (periodic law table the 1 family, the 2nd family, the 3rd family) and the halogen element, 0＜p≤1,1≤q≤3,1≤r≤8); Li
(s)Fe
2O
3(in the formula, 0≤s≤1); Li
(t)WO
2Compounds such as (in the formulas, 0≤t≤1).As the metal oxide that negative material relates to, for example, can enumerate GeO, GeO
2, SnO, SnO
2, PbO, PbO
2, Pb
2O
3, Pb
3O
4, Sb
2O
3, Sb
2O
4, Sb
2O
5, Bi
2O
3, Bi
2O
4, Bi
2O
5As the electroconductive polymer that negative material relates to, can enumerate polyacetylene, polyparaphenylene etc.
The spacer that lithium secondary battery of the present invention relates to is the insulating properties film with mechanical strength of big ion permeability and regulation.As spacer,, can use sheet material or the nonwoven fabrics made by olefin polymers such as polypropylene, glass fibre or polyethylene etc. from organic solvent resistance and hydrophobic viewpoint.The aperture of the spacer that lithium secondary battery of the present invention relates to for example is 0.01～10 μ m for the useful scope of using as general battery gets final product.The thickness of the spacer that lithium secondary battery of the present invention relates to for example is 5～300 μ m for the scope of using as general battery gets final product.In addition, when using the solid electrolyte as electrolytical polymer etc. described later, solid electrolyte double as spacer.
The nonaqueous electrolyte that contains the lithium salts that lithium secondary battery of the present invention relates to comprises nonaqueous electrolyte and lithium salts.As the nonaqueous electrolyte that lithium secondary battery of the present invention relates to, can enumerate nonaqueous electrolytic solution, organic solid electrolyte based, inorganic solid electrolyte.The nonaqueous electrolytic solution that relates to as nonaqueous electrolyte, for example, can enumerate the N-N-methyl-2-2-pyrrolidone N-, propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), 1, the 3-dioxolanes, formamide, dimethyl formamide, dioxolanes, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 3-methyl-2-oxazolidone, 1,3-dimethyl-2-imidazolone, the propylene carbonate ester derivant, tetrahydrofuran derivatives, diethyl ether, 1, the 3-N-morpholinopropanesulfonic acid lactone, methyl propionate, the non-proton organic solvent of ethyl propionate etc., these can be independent a kind or make up more than 2 kinds and use.
The organic solid electrolyte based that relates to as nonaqueous electrolyte, for example, can enumerate polythene derivative, polyethylene oxide derivant or the derivative, phosphate ester polymer, polyphosphazene, polyaziridine, polyvinyl sulfide, polyvinyl alcohol, Kynoar, polyhexafluoropropylene etc. that have polymer, the poly propylene oxide derivative of poly(ethylene oxide) base or have a PPOX base have the mixture etc. of the polymer of the ionic base that dissociates, the polymer with the ionic base that dissociates and the nonaqueous electrolytic solution that above-mentioned nonaqueous electrolyte relates to.
As the inorganic solid electrolyte that nonaqueous electrolyte relates to, can enumerate nitride, halide, oxysalt of Li etc., for example, can enumerate Li
3N, LiI, Li
5NI
2, Li
3N-LiI-LiOH, LiSiO
4, LiSiO
4-LiI-LiOH, Li
2SiS
3, Li
4SiO
4, Li
4SiO
4-LiI-LiOH, Li
3PO
4-Li
2S-SiS
2, phosphoric sulfide compound etc.
As the lithium salts that lithium secondary battery of the present invention relates to, can be set forth in the lithium salts that dissolves in the nonaqueous electrolyte that the lithium secondary battery of the invention described above relates to, for example, can enumerate LiCl, LiBr, LiI, LiClO
4, LiBF
4, LiB
10Cl
10, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, LiAlCl
4, CH
3SO
3Li, CF
3SO
3Li, (CF
3SO
2)
2NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, tetraphenyl lithium borate, acid imide etc., these can be independent a kind or make up more than 2 kinds and use.
The nonaqueous electrolyte that lithium secondary battery of the present invention relates to for the purpose of improving discharge, charge characteristic, anti-flammability, can contain compound shown below.As such compound, for example, can enumerate pyridine, triethyl phosphorite, triethanolamine, cyclic ethers, ethylenediamine, positive glyme, six tricresyl phosphate acid amides, nitrobenzene derivative, sulphur, quinoneimine dye, N-substituted oxazolidinone and N, the N-substituted imidazolinones, the ethylene glycol bisthioglycolate alkyl ether, ammonium salt, polyethylene glycol, the pyrroles, 2-methyl cellosolve, alchlor, the monomer of conductive polymer electrodes active material, TEF, trialkyl phosphine, morpholine, aryl compound with carbonyl, HMPA and 4-alkyl morpholine, the tertiary amine of two ring property, oil phosphonium salt is with the Shu phosphonium salt, phosphonitrile, carbonic ester etc.Particularly for the nonaqueous electrolyte electrolysis liquid that lithium secondary battery of the present invention is related to is noninflammability, the nonaqueous electrolyte that lithium secondary battery of the present invention relates to can contain for example Halogen solvent of carbon tetrachloride, trifluoro-ethylene etc.In addition, have the adaptability that high temperature is preserved in order to make lithium secondary battery of the present invention, the nonaqueous electrolyte that lithium secondary battery of the present invention relates to can contain carbon dioxide.
The lithium secondary battery of the present invention of Gou Chenging is the battery performance excellence like this, and particularly in using usually, discharge capacity descends difficult, demonstrates continuous change in voltage when discharging and recharging, and the few lithium secondary battery of the performance degradation that causes because of over-discharge can.
The shape of lithium secondary battery of the present invention can be shape arbitrarily such as button-type, sheet, cylindric, square, Coin shape.In addition, lithium secondary battery of the present invention can compatibly use in civil electronic device of for example electronic installation, automobile, electric car, game machines etc. such as notebook personal computer, pocket micro-personal computer, pocket word processor, mobile phone, wireless handset, pocket CD player, broadcast receiver, liquid crystal TV set, stand-by power supply, battery powered shaver, storage card, video camera etc.
Embodiment
Below, the present invention will be described in more detail by embodiment, but the invention is not restricted to these embodiment.
(embodiment 1)
(manufacturing of LiMn2O4)
Firing of＜manganese carbonate 〉
In nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire commercially available non-alkaline carbonic acid manganese (MnCO with 550 ℃
3, average grain diameter is 8.1 μ m) and 10 hours, obtain firing thing A (MnO).By XRD analysis the thing A that fires that obtains is analyzed, confirm as MnO.
In addition, in the 200mL beaker, take by weighing the above-mentioned commercially available non-alkaline carbonic acid manganese of 10g, add the 100g ultra-pure water, stirred 5 minutes at 25 ℃.Filter then, (the hole field makes society of institute and produces, and F-14) measures the pH of filtrate with pH meter.As a result, the pH of filtrate is 7.14.
＜MnO fires 〉
In air atmosphere (oxygen concentration is 21.0 volume %), fire as above-mentioned operation and obtain fired thing A (MnO) 10 hours obtains firing thing B (Mn with 650 ℃
2O
3).By XRD analysis the thing B that fires that obtains is analyzed, confirm as Mn
2O
3
Firing of＜reacting material mixture 〉
Is 0.99 mode with the Li atom with respect to the mol ratio (Li/Mn) of Mn atom, mixes as above-mentioned operation and obtain fire thing B (Mn
2O
3) and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C1.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C1 that obtains 10 hours with 700 ℃, obtain LiMn2O4 D1.In addition, confirm that the LiMn2O4 D1 that obtains is the single-phase LiMnO of expression ASTM card 23-361 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement 〉
Fill in the glass dish with cover of special use as above-mentioned operation and the LiMn2O4 D1 that obtains, (Japanese electric look society produces, and SE2000) measures 3 L to use the beam splitting type colour difference meter
*Value, a
*Value, b
*Value is obtained its mean value.Its result of expression in table 2.
＜evaluation of physical property 〉
Measure average grain diameter and the BET specific area of the LiMn2O4 D1 that obtains as above-mentioned operation.Its result of expression in table 2.
＜pH measures 〉
The LiMn2O4 D1 that obtains to 5g such as above-mentioned operation adds the 100g pure water, and 25 ℃ were stirred 5 minutes.After leaving standstill 5 minutes again, (the hole field makes society of institute and produces, and F-14) measures the pH of supernatant with pH meter.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The making of＜test cell 〉
Mix the powdered graphite of the LiMn2O4 D1, the 10 quality % that obtain as above-mentioned operation of 85 quality %, the Kynoar of 5 quality %, make cathode mixture, it is disperseed in N-methyl-2-methyl pyrrolidone, be modulated to mixing thickener.Dry, punching press behind the mixing thickener that obtains of coating on the aluminium foil are stamped into the disk of diameter 15mm, obtain positive plate.
Then, on the positive plate that obtains, make up each parts such as spacer, negative pole, collector plate, assembling metal parts, outside terminal, electrolyte, make test cell E1.Wherein, in negative pole, use the lithium metal, in collector plate, use copper, in electrolyte, use in 1 liter of ethylene carbonate and 1: 1 mixing liquid of methyl ethyl carbonate, to be dissolved with 1 mole of LiPF
6Solution.The mensuration of the initial stage charging capacity of＜test cell, initial stage discharge capacity and average charging tension 〉
CCCV pattern, open circuit voltage 4.25V, 2.5mA/cm are adopted in charging
2Current density, making breaking current is 1/20 of 1C electric current; CCCV pattern, open circuit voltage 3.4V, 2.5mA/cm are adopted in discharge
2Current density, making breaking current is 7/200 of 1C electric current, measures the average charging tension in initial stage charging capacity, initial stage discharge capacity and CC zone.Its result of expression in table 3.
Embodiment 2～12
(manufacturing of LiMn2O4)
Not adopting the Li atom is 0.99 mode mixed sintering thing B and Li with respect to the mol ratio (Li/Mn) of Mn atom
2CO
3, be mode mixed sintering thing B and Li with respect to the mol ratio (Li/Mn) of Mn atom in mol ratio shown in the table 1 but adopt the Li atom
2CO
3And, replacement was fired the reacting material mixture C1 that obtains 10 hours with 700 ℃ in nitrogen atmosphere (oxygen concentration is 0.01 volume %), but in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture (C2～C12) 10 hours that obtains with the firing temperature of expression in table 1, in addition, to carry out, obtain LiMn2O4 D2～D12 with embodiment 1 same method.In addition, confirm that the LiMn2O4 D2～D12 that obtains is the single-phase LiMnO of expression ASTM card 23-361 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D2～D12 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D2～D12 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 1)
(manufacturing of LiMn2O4)
Firing of＜manganese carbonate 〉
To carry out, obtain firing thing A with embodiment 1 same method.
＜MnO fires 〉
To carry out, obtain firing thing B with embodiment 1 same method.
Firing of＜reacting material mixture 〉
Is 0.85 mode with the Li atom with respect to the mol ratio (Li/Mn) of Mn atom, mixes as above-mentioned operation and obtain fire thing B and Li
2CO
3(average grain diameter 5 μ m) obtain reacting material mixture C13.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C13 that obtains 10 hours with 750 ℃, obtain LiMn2O4 D13.In addition, confirm that the LiMn2O4 D13 that obtains is the LiMnO of expression ASTM card 23-361 diffraction maximum figure
2, Mn
2O
3And Mn
3O
4Mixture.
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D13 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D13 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 2)
(manufacturing of LiMn2O4)
Not adopting the Li atom is 0.85 mode mixed sintering thing B and Li with respect to the mol ratio of Mn atom
2CO
3, but be 1.10 mode mixed sintering thing B and Li with respect to the mol ratio of Mn with the Li atom
2CO
3, in addition,, obtain LiMn2O4 D14 to carry out with comparative example 1 same method.In addition, confirm that the LiMn2O4 D14 that obtains is the LiMnO of expression ASTM card 23-361 diffraction maximum figure
2, Li
2MnO
3And Li
4Mn
5O
12Mixture.
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D14 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove and be substituted in the LiMn2O4 D1 that obtains among the embodiment 1, and use beyond the LiMn2O4 D14 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 3)
(manufacturing of LiMn2O4)
Firing of＜manganese carbonate 〉
To carry out, obtain firing thing A with embodiment 1 same method.
＜MnO fires 〉
To carry out, obtain firing thing B with embodiment 1 same method.
Firing of＜reacting material mixture 〉
Is 1.00 mode with the Li atom with respect to the mol ratio of Mn atom, mixes as above-mentioned operation and obtain fire thing B and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C15.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C15 that obtains 10 hours with 1000 ℃, obtain LiMn2O4 D15.In addition, confirm that the LiMn2O4 D15 that obtains is the single-phase LiMnO of expression ASTM card 72-0411 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D15 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D15 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 4)
(manufacturing of LiMn2O4)
Is that 1.00 mode is mixed commercially available MnO with the Li atom with respect to the mol ratio of Mn
2(average grain diameter is 3.5 μ m) and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C16.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C16 that obtains 10 hours with 800 ℃, obtain LiMn2O4 D16.In addition, confirm that the LiMn2O4 D16 that obtains is the single-phase LiMnO of expression ASTM card 72-0411 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D16 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D16 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 5)
In air atmosphere (oxygen concentration is 21.0 volume %), fire commercially available MnO with 1000 ℃
2(average grain diameter is 3.5 μ m) 12 hours obtains firing thing F17 (Mn
3O
4).Then, in air atmosphere (oxygen concentration is 21.0 volume %), with 650 ℃ fire obtain fired thing F17 10 hours, obtain firing thing G17 (Mn
2O
3).Is 1.00 mode with the Li atom with respect to the mol ratio of Mn atom, mix obtain fire thing G17 and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C17.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C17 that obtains 10 hours with 750 ℃, obtain LiMn2O4 D17.In addition, confirm that the LiMn2O4 D17 that obtains is the single-phase LiMnO of expression ASTM card 23-361 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1.And use beyond the LiMn2O4 D17 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D17 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 6)
In air atmosphere (oxygen concentration is 21.0 volume %), fire commercially available MnO with 600 ℃
2(average grain diameter is 3.5 μ m) 10 hours obtains firing thing H18 (Mn
2O
3).Then, be 1.00 mode with the Li atom with respect to the mol ratio of Mn atom, mix obtain fire thing H18 and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C18.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C18 that obtains 10 hours with 800 ℃, obtain LiMn2O4 D18.In addition, confirm that the LiMn2O4 D18 that obtains is the single-phase LiMnO of expression ASTM card 23-361 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D18 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D18 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
(comparative example 7)
In air atmosphere (oxygen concentration is 21.0 volume %), fire commercially available MnO with 600 ℃
2(average grain diameter is 3.5 μ m) 5 hours obtains firing thing I19 (Mn
2O
3).Then, be 1.00 mode with the Li atom with respect to the mol ratio of Mn, mix obtain fire thing I19 and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C19.Then, the reacting material mixture C19 that obtains is joined in the alumina crucible, with 1L/ minute feed speed air supply in alumina crucible, simultaneously be warmed up to 600 ℃ with 200 ℃/hour programming rate, then, air is switched to nitrogen, in alumina crucible, supply with 1L/ minute feed speed, simultaneously be warmed up to 800 ℃ with 200 ℃/hour programming rate, remain on 800 ℃ 10 hours.Then, in alumina crucible, import nitrogen, simultaneously with 200 ℃/hour cooling rate cool to room temperature with 1L/ minute feed speed.Then, product is pulverized, obtained LiMn2O4 D19.In addition, confirm that the LiMn2O4 D19 that obtains is the single-phase LiMnO of expression ASTM card 72-0411 diffraction maximum figure
2
(rerum natura of LiMn2O4)
＜color difference measurement, evaluation of physical property and pH measure 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D19 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 2.
(as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
The mensuration of the initial stage charging capacity of the making of＜test cell and test cell, initial stage discharge capacity and average charging tension 〉
Remove the LiMn2O4 D1 that replacement obtains in embodiment 1, and use beyond the LiMn2O4 D19 that obtains as above-mentioned operation, to carry out with embodiment 1 same method.Its result of expression in table 3.
[table 1]
| The Li/Mn ratio | The firing temperature of reacting material mixture (℃) | LiMn2O4 | ||
| Kind | X-ray diffraction peak figure | |||
| Embodiment 1 | 0.99 | 700 | D1 | 23-361 |
| Embodiment 2 | 1.00 | 700 | D2 | 23-361 |
| Embodiment 3 | 1.01 | 700 | D3 | 23-361 |
| Embodiment 4 | 0.99 | 750 | D4 | 23-361 |
| Embodiment 5 | 1.00 | 750 | D5 | 23-361 |
| Embodiment 6 | 1.01 | 750 | D6 | 23-361 |
| Embodiment 7 | 0.99 | 800 | D7 | 23-361 |
| Embodiment 8 | 1.00 | 800 | D8 | 23-361 |
| Embodiment 9 | 1.01 | 800 | D9 | 23-361 |
| Embodiment 10 | 0.99 | 850 | D10 | 23-361 |
| Embodiment 11 | 1.00 | 850 | D11 | 23-361 |
| Embodiment 12 | 1.01 | 850 | D12 | 23-361 |
| Comparative example 1 | 0.85 | 750 | D13 | 23-361 |
| Comparative example 2 | 1.10 | 750 | D14 | 23-361 |
| Comparative example 3 | 1.00 | 1000 | D15 | 72-0411 |
| Comparative example 4 | 1.00 | 800 | D16 | 72-0411 |
| Comparative example 5 | 1.00 | 750 | D17 | 23-361 |
| Comparative example 6 | 1.00 | 800 | D18 | 23-361 |
| Comparative example 7 | 1.00 | 800 | D19 | 72-0411 |
| Comparative example 10 | 1.00 | 800 | D20 | 72-0411 |
[table 2]
| LiMn2O4 | Average grain diameter (μ m) | BET specific area (m 2/g) | PH during aqueous dispersion | The color difference measurement value | |||
| L * | a * | b * | |||||
| Embodiment 1 | D1 | 13.6 | 0.74 | 11.2 | 28.4 | -0.52 | 6.66 |
| Embodiment 2 | D2 | 13.2 | 0.74 | 11.2 | 28.3 | -0.47 | 6.80 |
| Embodiment 3 | D3 | 13.8 | 0.8 | 11.3 | 28.5 | -0.38 | 6.77 |
| Embodiment 4 | D4 | 13.9 | 0.66 | 11.2 | 28.0 | -0.71 | 6.31 |
| Embodiment 5 | D5 | 14.2 | 0.65 | 11.2 | 28.0 | -0.61 | 6.41 |
| Embodiment 6 | D6 | 14.1 | 0.69 | 11.3 | 28.3 | -0.56 | 6.57 |
| Embodiment 7 | D7 | 14.1 | 0.68 | 11.2 | 27.7 | -0.71 | 6.10 |
| Embodiment 8 | D8 | 13.9 | 0.71 | 11.3 | 27.8 | -0.73 | 6.13 |
| Embodiment 9 | D9 | 13.9 | 0.68 | 11.3 | 27.6 | -0.68 | 5.82 |
| Embodiment 10 | D10 | 14.3 | 0.7 | 11.2 | 27.5 | -0.72 | 5.95 |
| Embodiment 11 | D11 | 14.8 | 0.6 | 11.2 | 27.6 | -0.84 | 5.97 |
| Embodiment 12 | D12 | 14.6 | 0.71 | 11.2 | 27.5 | -0.75 | 5.71 |
| Comparative example 1 | D13 | 13 | 0.85 | 10.2 | 28.9 | -0.04 | 6.27 |
| Comparative example 2 | D14 | 15 | 0.51 | 12 | 28.2 | 0.53 | 5.39 |
| Comparative example 3 | D15 | 13.4 | 0.49 | 10.6 | 22.6 | -0.75 | 1 5.9 |
| Comparative example 4 | D16 | 4.72 | 1.03 | 10.6 | 22.2 | -7.44 | 14.7 |
| Comparative example 5 | D17 | 7.93 | 0.77 | 11.6 | 37.1 | -7.02 | 16.8 |
| Comparative example 6 | D18 | 4.43 | 0.97 | 11.7 | 33.6 | -6.76 | 14.4 |
| Comparative example 7 | D19 | 4.54 | 0.93 | 10.9 | 20.8 | -8.12 | 13.3 |
| Comparative example 10 | D20 | 17.3 | 0.52 | 10.9 | 22.2 | -6.61 | 14.0 |
[table 3]
| LiMn2O4 | Initial stage charging capacity (a) (mAH/g) | Initial stage discharge capacity (b) (mAH/g) | (a)-(b) (mAH/g) | Average charging tension (V) | |
| Embodiment 1 | D1 | 175.1 | 29.9 | 145.2 | 3.81 |
| Embodiment 2 | D2 | 176.4 | 30.9 | 145.5 | 3.81 |
| Embodiment 3 | D3 | 172.7 | 29.6 | 143.1 | 3.82 |
| Embodiment 4 | D4 | 180.1 | 33.1 | 147.0 | 3.83 |
| Embodiment 5 | D5 | 182.3 | 33.8 | 148.5 | 3.81 |
| Embodiment 6 | D6 | 175.8 | 30.2 | 145.6 | 3.85 |
| Embodiment 7 | D7 | 179.6 | 32.0 | 147.6 | 3.83 |
| Embodiment 8 | D8 | 181.1 | 32.2 | 148.9 | 3.83 |
| Embodiment 9 | D9 | 176.6 | 31.5 | 145.1 | 3.82 |
| Embodiment 10 | D10 | 172.5 | 29.3 | 143.2 | 3.84 |
| Embodiment 11 | D11 | 173.2 | 29.6 | 143.6 | 3.85 |
| Embodiment 12 | D12 | 170.1 | 28.8 | 141.3 | 3.86 |
| Comparative example 1 | D13 | 136.9 | 12.6 | 124.3 | 3.90 |
| Comparative example 2 | D14 | 124.6 | 11.5 | 113.1 | 3.88 |
| Comparative example 3 | D15 | 150.3 | 21.7 | 128.6 | 3.93 |
| Comparative example 4 | D16 | 142.1 | 21.3 | 120.8 | 3.92 |
| Comparative example 5 | D17 | 161.6 | 22.8 | 138.8 | 3.92 |
| Comparative example 6 | D18 | 154.0 | 20.7 | 133.3 | 3.91 |
| Comparative example 7 | D19 | 152.1 | 22.1 | 130.0 | 3.94 |
| Comparative example 10 | D20 | 158.1 | 24.1 | 134.0 | 4.00 |
In addition, in the mensuration of initial stage charging capacity, initial stage discharge capacity and the average charging tension of the making of above-mentioned test cell and test cell, show, the material that the charging capacity of test cell is big and discharge capacity is little, promptly, the charge/discharge capacity difference is big more, and is high more as the Li supply capacity of the secondary active material of positive pole.Usually, constitute the anodal main active material of positive active material, for example LiCoO
2Charging capacity be 165mAH/g, relative therewith, discharge capacity is about 160mAH/g, so the charge/discharge capacity difference is little.
In addition, the average charging tension of test cell is low, demonstrates from low-voltage and just can supply with Li, supplies with material and very excellent as Li.
In embodiment 1～12, the charge/discharge capacity difference is more than the great 140mAH/g, and in addition, average charging tension also is low to moderate below the 3.86V, and the LiMn2O4 that obtains as can be known is very excellent as the secondary active material of positive pole.On the other hand, in comparative example 1 and 2, can not obtain single-phase LiMnO
2, because the charge/discharge capacity difference is little, therefore the Li supply capacity is low as can be known.In addition, in comparative example 3～7, the charge/discharge capacity difference is little, the average charging tension height, and therefore the Li supply capacity is low as can be known.
Like this, as shown in Table 3, the initial stage charging capacity height of LiMn2O4 of the present invention, the difference of charge/discharge capacity are big, and average charging tension is low.And, the effect height that the fail safe when such LiMn2O4 makes over-discharge can improves.
(embodiment 13～15 and comparative example 8～9)
(modulation of lithium composite xoide)
The Co of weighing 40.0g
3O
4The Li of (average grain diameter is 5 μ m) and 8.38g
2CO
3(average grain diameter is 5 μ m) after fully mixing with dry type, fired 5 hours with 1000 ℃.After firing, thing is pulverized, classification with firing of obtaining, and obtains cobalt acid lithium J (LiCoO
2).The average grain diameter of the cobalt acid lithium J that obtains is 7.4 μ m, and the BET specific area is 0.38m
2/ g.
(manufacturing of lithium secondary battery)
With in the cooperation ratio shown in the table 4, be blended in the LiMn2O4 shown in the table 4 as the secondary active material of positive pole and as above-mentioned operation and the cobalt acid lithium J that obtains as the main active material of positive pole, obtain positive active material K20～24.Then, mix positive active material K20～24,6 quality % powdered graphites, the 3 quality % Kynoar of 91 quality %, make cathode mixture, it is dispersed in the N-N-methyl-2-2-pyrrolidone N-, prepare mixing thickener.Behind the mixing thickener that obtains of coating on the aluminium foil, dry, punching press are stamped into the disk of diameter 15mm, obtain positive plate.Each parts of the positive plate that combination obtains, spacer, negative pole, collector plate, assembling metal parts, outside terminal, electrolyte etc. are made lithium secondary battery P20～24.Wherein, in negative pole, use Delanium, in collector plate, use copper, in electrolyte, use in 1: 1 mixing liquid of 1 liter of ethylene carbonate and methyl ethyl carbonate, to be dissolved with 1 mole of LiPF
6Liquid.
＜over-discharge can test 〉
To lithium secondary battery P20～24 of making as above-mentioned operation, at 25 ℃ of electric currents with 1CmA, constant current charge is to 4.2V, then with the constant voltage charging of 4.2V after 3 hours, and the discharge capacity when measuring constant current discharge with 1CmA (below be designated as " discharge capacity that over-discharge can is preceding ") to 3.0V.Then, placed 2 days, carry out over-discharge can with the constant voltage of 0V.After the placement, with the constant current charge of 1CmA to 4.2V, then with the constant voltage charging of 4.2V after 3 hours, the discharge capacity when measuring constant current discharge with 1CmA (below be designated as " discharge capacity after the over-discharge can ") to 3.0V.Then, according to the ratio of the discharge capacity preceding of the discharge capacity after the test of following formula (3) calculating over-discharge can, obtain the capacity restoration rate with respect to the over-discharge can test.Its result of expression in table 4.In addition, the battery after the over-discharge can test is disintegrated, observe the copper of negative electrode collector and whether on positive pole, separate out.Its result of expression in table 4.
Capacity restoration rate=(discharge capacity before the discharge capacity after the over-discharge can test/over-discharge can test) * 100 (3)
[table 4]
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Comparative example 8 | Comparative example 9 | |
| Positive active material | |||||
| The use level (mass parts) of main active material (cobalt acid lithium J) | 100 | 100 | 100 | 100 | 100 |
| The kind use level (mass parts) of secondary active material LiMn2O4 | D2 10 | D5 10 | D8 10 | D17 10 | - - |
| Lithium secondary battery | P20 | P21 | P22 | P23 | P24 |
| The over-discharge can result of the test | |||||
| Discharge capacity (mAh) before the over-discharge can test | 1.107 | 1.103 | 1.111 | 1.108 | 1.164 |
| Capacity restoration rate (%) | 94 | 94 | 94 | 87 | 29 |
| Cu separates out | Do not have | Do not have | Do not have | Do not have | Roughly separate out in front |
As shown in Table 4, LiMn2O4 of the present invention as anodal secondary active material, can be reduced the degradation that is caused by over-discharge can.
(comparative example 10)
(manufacturing of LiMn2O4)
Firing of＜manganese carbonate 〉
In nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire commercially available alkaline carbonic acid manganese (MnCO with 550 ℃
3, average grain diameter is 27.0 μ m) and 10 hours, obtain firing thing A20 (MnO).By XRD analysis the thing A20 that fires that obtains is analyzed, confirm as MnO.
In addition, in the 200mL beaker, take by weighing the above-mentioned alkaline carbonic acid manganese of 10g, add the 100g ultra-pure water, stirred 5 minutes at 25 ℃.Filter then, measure the pH of filtrate with pH meter.As a result, the pH of filtrate is 8.11.
＜MnO fires 〉
In air atmosphere (oxygen concentration is 21.0 volume %), fire as what above-mentioned operation obtained with 650 ℃ and to fire thing A20 (MnO) 10 hours, obtain firing thing B20 (Mn
2O
3).By XRD analysis the thing B20 that fires that obtains is analyzed, confirm as Mn
2O
3
Firing of＜reacting material mixture 〉
Is 1.00 mode with the Li atom with respect to the mol ratio (Li/Mn) of Mn atom, mixes as above-mentioned operation obtains fires thing B20 (Mn
2O
3) and Li
2CO
3(average grain diameter is 5 μ m) obtains reacting material mixture C20.Then, in nitrogen atmosphere (oxygen concentration is 0.01 volume %), fire the reacting material mixture C20 that obtains 10 hours with 800 ℃, obtain LiMn2O4 D20.In addition, confirm that the LiMn2O4 D20 that obtains is the single-phase LiMnO of expression ASTM card 72-0411 diffraction maximum figure
2
(rerum natura of LiMn2O4 and as the performance evaluation of the secondary active material of cathode plate for lithium secondary battery)
Remove replacement LiMn2O4 D1, and use beyond the LiMn2O4 D20, to carry out with embodiment 1 same method.Its result of expression in table 2 and table 3.
Claims (8)
1. the secondary active material LiMn2O4 of a cathode plate for lithium secondary battery is characterized in that:
With following general formula (1) expression, at L
*a
*b
*L in the colour system
*Value is 25.0～32.0, a
*Be-1.50～-0.1 5, b
*Be 2.50～8.00,
Li
xMnO
2 (1)
In the formula, 0.90≤x≤1.05.
2. the secondary active material LiMn2O4 of cathode plate for lithium secondary battery as claimed in claim 1 is characterized in that:
Average grain diameter is 1～25 μ m.
3. the secondary active material LiMn2O4 of cathode plate for lithium secondary battery as claimed in claim 1 or 2 is characterized in that:
The BET specific area is 0.2～2.0m
2/ g.
4. as the secondary active material LiMn2O4 of each described cathode plate for lithium secondary battery in the claim 1～3, it is characterized in that:
The pH of the dispersion liquid when disperseing in water is below 12.
5. the manufacture method of a LiMn2O4 is characterized in that, comprising:
In the inactive gas atmosphere below oxygen concentration is 1 volume %, fire non-alkaline carbonic acid manganese with 500～800 ℃, obtain first operation of MnO,
In the atmosphere more than oxygen concentration is 10 volume %, fire with 525～950 ℃ and to carry out the MnO that this first operation obtains, obtain Mn
2O
3Second operation and
Is 0.90～1.05 mode with lithium atom with respect to the mol ratio of manganese atom, mixes and carries out the Mn that this second operation obtains
2O
3With lithium compound, obtain reacting material mixture, then in the inactive gas atmosphere below oxygen concentration is 1 volume %, fire this reacting material mixture with 600～950 ℃, obtain the 3rd operation of LiMn2O4.
6. cathode active material for lithium secondary battery is characterized in that:
Contain the lithium composite xoide that the secondary active material of each described cathode plate for lithium secondary battery is used LiMn2O4 and represented with following general formula (2) in the claim 1～4,
Li
(a)M
(1-b)A
(b)O
(c) (2)
In the formula, M represents to be selected from the metallic element more than a kind among Co and the Ni, and A represents to be selected from the metallic element more than a kind among Mg, Al, Ti, Zr, Fe, Cu, Zn, Sn, In, Ca, Ba, Sr and the Mn, 0.9≤a≤1.1,0≤b≤0.5,1.8≤c≤2.2.
7. cathode active material for lithium secondary battery as claimed in claim 6 is characterized in that:
Described lithium composite xoide is LiCoO
2
8. lithium secondary battery is characterized in that:
Claim 6 or 7 described cathode active material for lithium secondary battery are obtained as positive active material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006240241A JP5078113B2 (en) | 2006-09-05 | 2006-09-05 | Lithium manganate for positive electrode secondary active material for lithium secondary battery, method for producing lithium manganate for positive electrode secondary active material for lithium secondary battery, positive electrode active material for lithium secondary battery, and lithium secondary battery |
| JP2006240241 | 2006-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101140987A true CN101140987A (en) | 2008-03-12 |
Family
ID=39192812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101498245A Pending CN101140987A (en) | 2006-09-05 | 2007-09-05 | Lithium manganese oxide and manufacturing method thereof, lithium secondary cell and positive active materials |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5078113B2 (en) |
| KR (1) | KR20080022057A (en) |
| CN (1) | CN101140987A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807686A (en) * | 2010-03-30 | 2010-08-18 | 兰州金里能源科技有限公司 | Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery |
| CN101964428A (en) * | 2010-08-05 | 2011-02-02 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method of lamellar lithium manganese battery |
| CN102574697A (en) * | 2009-06-25 | 2012-07-11 | 日本碍子株式会社 | Positive electrode active material and lithium secondary battery |
| CN103367715A (en) * | 2012-04-09 | 2013-10-23 | 索尼公司 | Cathode active material, cathode, secondary battery, battery pack, and electric vehicle |
| CN110190277A (en) * | 2019-06-06 | 2019-08-30 | 电子科技大学 | A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof |
| CN111816869A (en) * | 2020-08-07 | 2020-10-23 | 深圳先进技术研究院 | Negative electrode material, negative electrode, potassium ion battery and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4794619B2 (en) * | 2008-12-26 | 2011-10-19 | Ｔｄｋ株式会社 | Method for producing positive electrode for lithium ion secondary battery, method for producing lithium ion secondary battery, and positive electrode for lithium ion secondary battery and lithium ion secondary battery |
| JP2010260733A (en) * | 2009-04-30 | 2010-11-18 | Murata Mfg Co Ltd | Manganese-containing lithium transition metal multiple oxide and method for producing the same |
| WO2011075921A1 (en) * | 2009-12-27 | 2011-06-30 | 深圳市振华新材料股份有限公司 | High manganese polycrystalline anode material, preparation method thereof and dynamic lithium ion battery |
| JP5434632B2 (en) * | 2010-01-28 | 2014-03-05 | 株式会社Ｇｓユアサ | Non-aqueous electrolyte secondary battery active material and non-aqueous electrolyte secondary battery |
| US9150427B2 (en) | 2010-10-06 | 2015-10-06 | Tosoh Corporation | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same |
| CN102646824A (en) * | 2012-01-31 | 2012-08-22 | 西安汇杰实业有限公司 | Lithium ion battery anode material and preparation method thereof |
| JP6288338B1 (en) | 2017-03-24 | 2018-03-07 | 住友大阪セメント株式会社 | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, lithium ion secondary battery |
| EP4138151A4 (en) | 2020-04-13 | 2024-01-17 | Lg Energy Solution Ltd | Method for evaluating quality of electrode and method for manufacturing electrode |
| CN112968166A (en) * | 2021-03-22 | 2021-06-15 | 安徽博石高科新材料股份有限公司 | Preparation method of lithium manganate positive electrode material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4441678B2 (en) * | 1997-08-18 | 2010-03-31 | 独立行政法人産業技術総合研究所 | Method for producing orthorhombic lithium manganese composite oxide particulate composition represented by LiMnO 2 |
| JP2000021405A (en) * | 1998-07-01 | 2000-01-21 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JP3495638B2 (en) * | 1999-03-29 | 2004-02-09 | 株式会社ジャパンエナジー | Fine-grained dimanganese trioxide for lithium secondary batteries and method for producing the same |
| JP2005231914A (en) * | 2004-02-17 | 2005-09-02 | Nippon Chem Ind Co Ltd | Method for manufacturing lithium manganate |
| JP2005235416A (en) * | 2004-02-17 | 2005-09-02 | Nippon Chem Ind Co Ltd | Lithium manganate for lithium secondary battery cathode sub active material, lithium secondary battery cathode active material, and lithium secondary battery |
| JP4319663B2 (en) * | 2005-03-22 | 2009-08-26 | 日本化学工業株式会社 | Lithium manganate, lithium secondary battery positive electrode secondary active material, lithium secondary battery positive electrode active material, and lithium secondary battery |
-
2006
- 2006-09-05 JP JP2006240241A patent/JP5078113B2/en not_active Expired - Fee Related
-
2007
- 2007-09-04 KR KR1020070089462A patent/KR20080022057A/en not_active Application Discontinuation
- 2007-09-05 CN CNA2007101498245A patent/CN101140987A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574697A (en) * | 2009-06-25 | 2012-07-11 | 日本碍子株式会社 | Positive electrode active material and lithium secondary battery |
| CN101807686A (en) * | 2010-03-30 | 2010-08-18 | 兰州金里能源科技有限公司 | Preparation method of spinel type lithium manganate with high crystallinity used in lithium ion battery |
| CN101964428A (en) * | 2010-08-05 | 2011-02-02 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method of lamellar lithium manganese battery |
| CN101964428B (en) * | 2010-08-05 | 2013-02-20 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method of lamellar lithium manganese battery |
| CN103367715A (en) * | 2012-04-09 | 2013-10-23 | 索尼公司 | Cathode active material, cathode, secondary battery, battery pack, and electric vehicle |
| CN103367715B (en) * | 2012-04-09 | 2017-08-11 | 索尼公司 | Positive active material, positive pole, secondary cell, battery pack and electric vehicle |
| CN110190277A (en) * | 2019-06-06 | 2019-08-30 | 电子科技大学 | A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof |
| CN110190277B (en) * | 2019-06-06 | 2022-05-03 | 电子科技大学 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
| CN111816869A (en) * | 2020-08-07 | 2020-10-23 | 深圳先进技术研究院 | Negative electrode material, negative electrode, potassium ion battery and preparation method thereof |
| WO2022027907A1 (en) * | 2020-08-07 | 2022-02-10 | 深圳先进技术研究院 | Negative electrode material, negative electrode, potassium ion battery and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5078113B2 (en) | 2012-11-21 |
| KR20080022057A (en) | 2008-03-10 |
| JP2008066028A (en) | 2008-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101140987A (en) | Lithium manganese oxide and manufacturing method thereof, lithium secondary cell and positive active materials | |
| CN105070896B (en) | Nickelic polynary positive pole material of secondary lithium batteries and preparation method thereof | |
| CN101765934B (en) | Positive electrode active material for lithium secondary battery, method for production thereof, and lithium secondary battery | |
| US7838148B2 (en) | Lithium nickel manganese cobalt composite oxide used as cathode active material for lithium rechargeable battery, manufacturing method thereof, and lithium rechargeable battery | |
| KR101184851B1 (en) | Positive Electrode Active Material of Lithium Secondary Battery, Process for Preparing the Same and Lithium Secondary Battery | |
| KR101045416B1 (en) | Lithium titanate powder, preparation method thereof, electrode and secondary battery comprising the same | |
| CN103189316B (en) | Lithium cobalt oxide, process for producing same, positive active material for lithium secondary battery, and lithium secondary battery | |
| CN103296272A (en) | Anode active substance for lithium secondary battery, method for manufacturing the same, and lithium secondary battery | |
| JP2006278341A (en) | Lithium ion nonaqueous electrolyte secondary cell | |
| CN102576872A (en) | Positive electrode active material for lithium secondary battery, method for manufacturing the same, and lithium secondary battery | |
| CN102569722A (en) | Lithium ion secondary battery and anode thereof | |
| CN102498597A (en) | Positive electrode active material for lithium secondary batteries, production method for same and lithium secondary battery | |
| CN100521307C (en) | Lithium-cobalt composite oxides powder, its preparation method, lithium secondary cell and lithium secondary cell | |
| CN110235291A (en) | Positive electrode active materials, preparation method and the lithium secondary battery comprising it | |
| KR100854241B1 (en) | Lithium-Cobalt Based Combination Oxide, Process for Preparing the Same, Positive Electrode Active Material of Lithium Secondary Cell, and Lithium Secondary Cell | |
| US20140065477A1 (en) | Positive active material composition for rechargeable lithium battery, and positive electrode and rechargeable lithium battery including same | |
| CN103296273B (en) | Manufacture method, positive active material for lithium secondary battery and the lithium secondary battery of cathode active material for lithium secondary battery | |
| JP4271488B2 (en) | Lithium cobalt based composite oxide, method for producing the same, lithium secondary battery positive electrode active material, and lithium secondary battery | |
| KR101754612B1 (en) | Positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same | |
| CN104282900A (en) | Positive active material, method of preparing same, and rechargeable lithium battery including same | |
| KR20210088494A (en) | Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same | |
| JP5508322B2 (en) | Lithium cobalt based composite oxide powder, lithium secondary battery positive electrode active material, and lithium secondary battery | |
| KR101631386B1 (en) | Negative Electrode Material For Lithuim Secondary Battery Using Lithuim-Titanium Oxide And Preparation Method Thereof | |
| KR20140018717A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20050082149A (en) | Lithium manganate for lithium secondary cell positive electrode sub-active material, lithium secondary cell positive electrode active material and lithium secondary cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20080312 |