CN106410131A - positive active material for lithium secondary battery, preparation method thereof, and the lithium secondary battery - Google Patents
positive active material for lithium secondary battery, preparation method thereof, and the lithium secondary battery Download PDFInfo
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- CN106410131A CN106410131A CN201610617321.5A CN201610617321A CN106410131A CN 106410131 A CN106410131 A CN 106410131A CN 201610617321 A CN201610617321 A CN 201610617321A CN 106410131 A CN106410131 A CN 106410131A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a positive active material for a lithium secondary battery, a preparation method thereof, and the lithium secondary battery, wherein the positive active material includes a lithium containing compound; a surface process layer formed on the lithium containing compound; the surface process layer includes, freely, more than two selected from Al(OH)3, a boron-containing compound, and a silicon-containing compound.
Description
Technical field
The present invention relates to positive active material for lithium secondary battery and preparation method thereof and the lithium secondary battery comprising it.
Background technology
In IT, electric automobile, energy accumulating device field, the energy device attracted attention most at present is the secondary electricity of lithium
Pond.Nineteen ninety, after Sony realizes the commercialization of lithium secondary battery first, the past obtained over 25 years brilliance send out
Exhibition.Initial application is confined to such as the field of mobile equipment of notebook computer etc., but, it is applicable not only to electronic vapour at present
Car, and the scope of application has been also extend to extensive energy accumulating device.Especially, with emphasis environmental protection and efficiency, the secondary electricity of lithium
The suitable application area in pond expands the electric automobile field and energy accumulating device field as new industrial field to, and it is suitable for neck
Domain is just in rapid expansion.
If being originally adapted for lithium secondary battery simple realization life-span and the capacity goals of IT, can be suitable for, but, with
The application of lithium secondary battery expands electric automobile and energy accumulating device field to, for raising lithium secondary battery performance
Require persistently to increase, in this field, need to make capacity and life characteristic reach very high target, and also need to make thermally-stabilised
Property, that reliability, price also reach high target is just applicable.
Between 25 years of past, the positive active material of lithium secondary battery has obtained great development.In order to improve capacity,
From lithium-cobalt class compound (LiCoO2) start Persisting exploitation to lithium, nickel, cobalt, manganese class compound (LiNixCoyMnzO2、x：y：Z=
1：1：1、4：3：3、5：2：3、6：2：2、8：1：1), additionally, going back Persisting exploitation as the lithium-nickel-cobalt-aluminium class of ultra-high capacity positive pole
Compound (LiNixCoyAlzO2, x be equal to 80,83,85,88), and the scope of application also can continuous enlargement.Generally, whole in order to strengthen
Body structure, applies more than one transition metal-type by the sandwich layer in positive active material and forms the stable core of overall structure
Layer, implements to improve life characteristic, heat endurance, reliability etc. further to be surface-treated.For example, in lithium-cobalt compound
In the case of, being formed makes LiCo1-x-yM'xM"yO2The sandwich layer of the overall structure stabilisation of form using, by apply M'=Mg,
The metal of M "=Ti etc. is using.Like this, in order to improve life characteristic, heat endurance, reliability etc., overall structure is obtained
Lithium-cobalt class compound to stabilisation implements surface treatment.The exploitation of above-mentioned coating technology is applicable not only to lithium-cobalt class chemical combination
Thing, and apply also for lithium-manganese class compound, lithium, nickel, cobalt, manganese class compound, lithium-nickel-cobalt-aluminium class compound etc..
In the lithium secondary battery, the method improving battery capacity is broadly divided into two kinds.One kind is to be suitable for high power capacity positive pole to live
Property the method to develop lithium secondary battery for the material, another kind be by improve lithium secondary battery charging voltage make battery Gao Rong
The method quantifying.In the case of first method, to lithium-cobalt class compound (discharge capacity 160mAh/g) → LNCM (electric discharge
Capacity 180mAh/g) direction of → LNCA (discharge capacity 200mAh/g) develops and is suitable for high power capacity positive active material, thus
The method developing lithium secondary cell with high capacity.In the case of second method, for using identical type positive electrode active material
Matter simultaneously develops the developing way of lithium secondary cell with high capacity.In addition to lithium-manganese class compound, general positive active material is in layer
Shape structure, therefore, if improving charging voltage, discharge capacity can increase.For example, in the case of lithium-cobalt class compound, if with
4.3V is charged and discharges, then can present 160mAh/g about discharge capacity, if being charged with 4.4V and discharging, can
Present 170mAh/g about discharge capacity, if being charged with 4.5V and discharging, can present 180mAh/g about electric discharge
Capacity.That is, it is developed recently and with high voltage, lithium secondary battery is filled using the characteristic of above-mentioned layered cathode active material
The technology of electricity, thus develops the lithium secondary battery of high power capacity.But, if by improve positive active material charging voltage Lai
Evaluate its performance, then charging voltage is higher, discharge capacity increases, but, present the phenomenon that life characteristic drastically declines on the contrary,
And, charging voltage is higher, heat endurance (Thermal stability：The characteristic directly related with the stability of battery) more
Difference.And, with normal temperature phase ratio, above-mentioned phenomenon is more serious at high temperature.That is, if carrying out height using by improving charging voltage
The lithium secondary battery that voltage charges, then charging voltage is higher, and normal temperature phase ratio, at high temperature, the life characteristic of lithium secondary battery,
Heat endurance, reliability etc. are poorer.
Content of the invention
It is an object of the invention to, positive active material for lithium secondary battery etc., above-mentioned positive electrode for lithium secondary battery are provided
Active material comprises：Lithium-containing compound；And surface-treated layer, it is formed on above-mentioned lithium-containing compound, above-mentioned surface-treated layer
Comprise selected from Al (OH)3, boride alloy and compound containing Si composition group in two or more compounds.
But, the technical problem to be solved is not limited to problems noted above, the affiliated technology of the present invention
The those of ordinary skill in field can be expressly understood that NM other problemses from following record.
The present invention provides positive active material for lithium secondary battery, and positive active material for lithium secondary battery comprises：Containing lithium
Compound；And surface-treated layer, it is formed on above-mentioned lithium-containing compound, above-mentioned surface-treated layer comprises selected from Al (OH)3、
Two or more compound in the group of boride alloy and the composition of compound containing Si.
Above-mentioned lithium-containing compound can comprise selected from lithium, nickel, cobalt, manganese class compound, lithium-nickel-cobalt-aluminium class compound and
The compound of one or more of the group of lithium-cobalt class compound composition.
Above-mentioned lithium-containing compound can be the following lithium, nickel, cobalt, manganese class compound stating chemical formula 1 expression：
Chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In above-mentioned formula, 0.95≤x≤1.1,0.05≤y≤0.2,0.05≤z≤0.3,0≤a≤0.04, M be selected from
One or more of group being made up of Mg, Ti, Al and Zr, A is in the group selected from O, F, S and P composition.
Above-mentioned surface-treated layer can comprise Al (OH)3, boride alloy and compound containing Si, or Al (OH) can be comprised3And
Boride alloy, or Al (OH) can be comprised3And compound containing Si, or boride alloy and compound containing Si can be comprised.
Comprise Al (OH) in above-mentioned surface-treated layer3, in the case of boride alloy and compound containing Si, with respect to 100 weights
The Al (OH) of amount part3, the boride alloy of 20 weight portions to 100 weight portions and 30 weight portions to 100 weight portions can be comprised containing Si
Compound.
In the particle of above-mentioned positive active material is distributed, when by a diameter of for 50% mass accumulation particle size distribution D50
When, D50 can be 5 μm～7 μm.
As an example of the present invention, the present invention provides the preparation method of positive active material for lithium secondary battery, above-mentioned
The preparation method of positive active material for lithium secondary battery includes：Step a, prepares lithium-containing compound；Step b, preparation comprises to select
Free Al (OH)3The surface of the two or more solution in the group of solution, boride alloy solution and the composition of compound solution containing Si
Processing solution；And step c, it is added to, to the lithium-containing compound preparing in above-mentioned steps a, the table preparing in above-mentioned steps b
After the processing solution of face, mixed and be dried.
In above-mentioned steps b, Al (OH)3Solution, boride alloy solution or compound solution containing Si can by water or 95% with
Under ethanol to use as solvent.
In above-mentioned steps b, Al (OH)3In solution, boride alloy solution or compound solution containing Si, each solute is dense
Degree can be 1ppm to 1000ppm.
In above-mentioned steps c, the weight ratio of surface processing solution and lithium-containing compound can be 0.5：1 to 1：3.
In above-mentioned steps c, mixing can be executed simultaneously and be dried.
In above-mentioned steps c, mixing and drying can execute 1 hour to 10 hours at a temperature of 50 DEG C to 150 DEG C.
The present invention may also include step d, carries out adding at heat at a temperature of higher than the baking temperature in above-mentioned steps c
Reason.
Above-mentioned additional heat treatment can execute 1 hour to 10 hours at a temperature of 100 DEG C to 700 DEG C.
As another example of the present invention, the present invention provides the lithium secondary battery comprising above-mentioned positive active material.
The positive active material for lithium secondary battery of the present invention is characterised by, comprises：Lithium-containing compound；And at surface
Reason layer, is formed on above-mentioned lithium-containing compound, above-mentioned surface-treated layer comprises selected from Al (OH)3, boride alloy and contain Siization
Two or more compound in the group of compound composition, is surface-treated to lithium-containing compound by multiple compounds, thus,
Under high voltage condition, lithium secondary battery has high temperature and normal temperature life characteristic improves, heat endurance improves and expansion characteristics carry
High effect.
Brief description
Fig. 1 is the chart of the thermal characteristics illustrating boride alloy.
Fig. 2 is that can simultaneously execute in the preparation method of the positive active material being shown in the present invention mixes and dry dress
The photo put.
Fig. 3 is the electron scanning micrograph of the positive active material observing the present invention.
Fig. 4 is the chart of the X diffraction crystalline texture of positive active material of the analysis present invention.
Fig. 5 a to Fig. 5 e is the button cell of the positive active material illustrating to comprise the present invention and the normal temperature longevity of fuel cell
The chart of life characteristic.
Fig. 6 a to Fig. 6 f is the button cell of the positive active material illustrating to comprise the present invention and the high temperature longevity of fuel cell
The chart of life characteristic.
Fig. 7 is the capacity retention of the C-rate change of the button cell of the positive active material illustrating to comprise the present invention
Chart.
Fig. 8 is the chart of the heat endurance of the button cell of the positive active material illustrating to comprise the present invention.
Fig. 9 is the chart of the expansion characteristics of the fuel cell of the positive active material illustrating to comprise the present invention.
Figure 10 is whether basis compares, to lithium-containing compound coating element-specific, the positive active material comprising the present invention
The life characteristics at high temperature of button cell chart.
Figure 11 is to compare, according to the amount determining element special to lithium-containing compound coating, the collection active matter comprising the present invention
The chart of the high output characteristic of C-rate change of the fuel cell of matter.
Specific embodiment
At present, lithium secondary battery is applicable not only to IT field, and applies also for electric automobile, energy accumulating device field
Deng thus the suitable application area of lithium secondary battery drastically expands.Now, in the case of IT lithium secondary battery, the battery longevity
Order and just be enough to for 300 times about, but, in the case of lithium secondary battery used for electric vehicle, at high temperature, battery life needs
Meet 1000～2000 times about, in the case of energy accumulating device lithium secondary battery, need to ensure 10 years about make
Use the time.
The present inventor is in order to lithium secondary battery is applied to IT field, electric automobile field, energy storage field, right
Process for treating surface for improving the life-span of lithium secondary battery and the positive active material of reliability properties is studied,
In the case of lithium-containing compound being surface-treated by multiple compounds, especially, under high voltage and hot conditions, confirm
The life characteristic of lithium secondary battery can be improved, the present invention is completed with this.
Hereinafter, describe the present invention in detail.
The present invention provides positive active material for lithium secondary battery, and above-mentioned positive active material for lithium secondary battery includes：
Lithium-containing compound；And surface-treated layer, it is formed on above-mentioned lithium-containing compound, above-mentioned surface-treated layer comprises selected from Al
(OH)3, boride alloy and compound containing Si composition group in two or more compounds.
Above-mentioned lithium-containing compound is corresponding with the sandwich layer of positive electrode active material layer, and above-mentioned lithium-containing compound may include and is selected from
One or more of the group of lithium, nickel, cobalt, manganese class compound, lithium-nickel-cobalt-aluminium class compound and lithium-cobalt class compound composition
Compound.Above-mentioned lithium-containing compound is in layer structure, therefore, if improving charging voltage, can increase discharge capacity, thus existing
Reduce the problem of the life characteristic of secondary cell, so that for the technology improving the problems referred to above.Especially it is preferable that above-mentioned
Lithium-containing compound for nickel content be 30～90% lithium, nickel, cobalt, manganese class compound or lithium-nickel that nickel content is 80～88%-
Cobalt-aluminium class compound, but be not limited thereto.Now, nickel content is higher, there is a problem of that heat endurance reduces, so that
For improving the process for treating surface of the problems referred to above.
Specifically, above-mentioned lithium-containing compound can be the following lithium, nickel, cobalt, manganese class compound stating chemical formula 1 expression：
Chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In above-mentioned formula, 0.95≤x≤1.1,0.05≤y≤0.2,0.05≤z≤0.3,0≤a≤0.04, M be selected from
One or more of group being made up of Mg, Ti, Al and Zr, A is selected from the group of O, F, S and P composition.
Specifically, above-mentioned M is based on coating and is added, in the case of applying M to above-mentioned lithium-containing compound, in high voltage
Under the conditions of, lithium secondary battery has the effect of life characteristics at high temperature raising.
Now, it is preferable that M is 0.001≤a≤0.02 in the case of independent coating M, in the situation of the composite coating of M
Down it is preferable that M is 0.001≤a≤0.04, but it is not limited thereto.As above adjust the M amount to the coating of above-mentioned lithium-containing compound,
Thus, lithium secondary battery can guarantee high output characteristic in High C-rate.
Above-mentioned surface-treated layer can comprise Al (OH)3, boride alloy and compound containing Si, or Al (OH) can be comprised3And
Boride alloy, or Al (OH) can be comprised3And compound containing Si, or boride alloy and compound containing Si can be comprised.That is, on
State surface-treated layer and comprise multiple compounds, therefore, under high voltage condition, lithium secondary battery has high temperature and the normal temperature life-span is special
Property improve, heat endurance improve and expansion characteristics improve effect.
Specifically, in the present invention, as in the multiple compounds for being surface-treated to lithium-containing compound
Kind, Al (OH) can be comprised3.Aluminum contained compound is used for the stability of the structure of positive active material, and aluminum contained compound plays and passes through
The combination of reinforced metal and oxygen is strengthening the effect of integrated structure.Especially, in aluminum contained compound, Al (OH)3Crystallization can be made
Structure stabilization, and the surface impedance of positive active material can be reduced, thus extremely advantageous.
And, in the present invention, as one of multiple compounds for being surface-treated to lithium-containing compound,
Boride alloy can be comprised.Now it is preferable that boride alloy is used for improving the heat endurance of lithium secondary battery, boride alloy can
Selected from the B assuming heat absorption characteristic at a temperature of about 160～200 DEG C about2O3、HB(OH)2And H3BO3In the group of composition,
Most preferably, boride alloy is HB (OH)2, but be not limited thereto.Now, can be by B2O3After being dissolved in water or ethanol,
Carry out heat treatment to obtain HB (OH) in about 100 DEG C2, HB (OH)2Present and absorb at a temperature of about 200 DEG C about
The characteristic of amount of heat.
Fig. 1 is the chart of the thermal characteristics illustrating boride alloy.
As shown in figure 1, dsc analysis result, boride alloy presents and absorbs at a temperature of about 160～200 DEG C about
The characteristic of heat, if to comprise chemical combination containing B as one of multiple compounds for being surface-treated to lithium compound
Thing, then can improve the heat endurance of lithium secondary battery to a great extent.
And, in the present invention, as one of multiple compounds for being surface-treated to lithium-containing compound,
Compound containing Si can be comprised.At high temperature, the major reason that the life characteristic of lithium secondary battery drastically declines is by electrolyte
The metal ingredient (Ni, Co, Mn etc.) that the HF that reaction with moisture in electrolyte is generated attacks positive active material carrys out dissolution gold
Belong to.Now, compound containing Si and HF have outstanding reactivity, therefore make lithium-containing compound and HF cannot be carried out reacting.Specifically
Ground, compound containing Si can be Si or SiO2.
That is, comprise Al (OH) in above-mentioned surface-treated layer3, in the case of boride alloy and compound containing Si, all can ensure that
The stabilisation of crystalline texture and low surface impedance, heat endurance and life characteristic outstanding at high temperature.
Comprise Al (OH) in above-mentioned surface-treated layer3, in the case of boride alloy and compound containing Si, with respect to 100 weights
The Al (OH) of amount part3, the boride alloy of 20 weight portions to 100 weight portions and 30 weight portions to 100 weight portions can be comprised containing Si
Compound.
Comprise Al (OH) in above-mentioned surface-treated layer3And in the case of boride alloy, with respect to the Al of 100 weight portions
(OH)3, the boride alloy of 100 weight portions of 20 weight portions can be comprised.
Comprise Al (OH) in above-mentioned surface-treated layer3And in the case of compound containing Si, with respect to the Al of 100 weight portions
(OH)3, 30 weight portions can be comprised to the compound containing Si of 100 weight portions.
In the case that above-mentioned surface-treated layer comprises boride alloy and compound containing Si, with respect to the Al of 100 weight portions
(OH)3, 50 weight portions can be comprised to the compound containing Si of 200 weight portions.
In the particle distribution of above-mentioned positive active material, when by a diameter of for 50% mass accumulation particle size distribution D50,
Compared with the big particle being 11 μm～13 μm with D50, D50 is 5 μm～7 μm of small particles in life characteristics at high temperature and high output characteristic
Aspect is improved, but is not limited thereto.
And, the present invention provides the preparation method of positive active material for lithium secondary battery, and above-mentioned secondary lithium batteries are just
The preparation method of pole active material includes：Step a, prepares lithium-containing compound；Step b, preparation comprises selected from Al (OH)3Molten
The surface processing solution of the two or more solution in the group of liquid, boride alloy solution and the composition of compound solution containing Si；And
Step c, in above-mentioned steps a prepare lithium-containing compound be added in above-mentioned steps b prepare surface processing solution it
Afterwards, mixed and be dried.
First, in order to prepare positive active material for lithium secondary battery, prepare lithium-containing compound (step a).Contain to above-mentioned
The explanation of lithium compound is as above.
Then, in order to prepare positive active material for lithium secondary battery, preparation comprises selected from Al (OH)3Solution, contain Bization
Surface processing solution (the step b) of the two or more solution in the group of polymer solution and the composition of compound solution containing Si.
Above-mentioned Al (OH)3Solution, boride alloy solution or solution containing Si can using water or less than 95% ethanol as solvent
To use.If will be greater than the 95% high ethanol of purity to use as solvent, there is the longevity that cannot bring lithium secondary battery
Life and the problem of reliability properties raising.In the present invention, by B2O3The aqueous solution to use as boride alloy solution, is inciting somebody to action
B2O3After being dissolved in water, it is heat-treated at a temperature of about 100 DEG C, thus the HB as boride alloy can be obtained
(OH)2.
At above-mentioned Al (OH)3In solution, boride alloy solution or compound solution containing Si, the concentration of each solute is permissible
For 1ppm to 1000ppm.Now, at Al (OH)3In solution, boride alloy solution or compound solution containing Si, each solute
Concentration maintains 1ppm to 1000ppm, thus, has and carrys out reduces cost by using a small amount of surface treatment substance and make lithium secondary
The advantage of the performance maximization of battery.
Then, in order to prepare positive active material for lithium secondary battery, provide positive active material for lithium secondary battery
Preparation method, said method includes：Step c, is added in above-mentioned steps b to the lithium-containing compound preparing in above-mentioned steps a
After the surface processing solution of middle preparation, mixed and be dried.
Preferably, the weight of above-mentioned surface processing solution and lithium-containing compound is than for 0.5：1 to 1：3, but be not limited to
This.Now, surface processing solution and lithium-containing compound weight than less than 0.5：In the case of 1, because of surface processing solution
Deficiency, thus there is a problem of cannot be carried out uniformly being surface-treated, in the weight ratio of surface processing solution and lithium-containing compound
More than 1：In the case of 3, excessive because of surface processing solution, and dry run consumes the excessive time, thus there is economy asking
Topic.
Above-mentioned mixing and drying can be executed simultaneously.As described above, in order to execute mixing and be dried simultaneously, Fig. 2 institute can be used
The device showing.Said apparatus are characterised by can implementing to be surface-treated simultaneously and being dried.
And specifically, it is preferable to ground, above-mentioned mixing and dry execution 1 hour to 10 hours at a temperature of 50 DEG C to 150 DEG C, but
It is not limited thereto.Now, mix and above range at a temperature of execution is dried, thus there is the minimum based on equipment investment
The advantage of the simplification of change and operation.
Optionally, in order to prepare positive active material for lithium secondary battery, the present invention may also include step d, than on
State the baking temperature in step c higher at a temperature of carry out add heat treatment.
And specifically, it is preferable to ground, above-mentioned additional heat treatment execution 1 hour to 10 hours in 100 DEG C to 700 DEG C of temperature,
But it is not limited thereto.Now, add heat treatment at a temperature of above range execute above range time, thus, than
At a temperature of relatively low, the heat treatment of execution short time, thus have the advantages that economic aspect.
And, the present invention provides the lithium secondary battery comprising above-mentioned positive active material.
Specifically, above-mentioned positive active material can provide lithium secondary battery, and above-mentioned lithium secondary battery includes：Positive pole, including
Conductive material and binding agent；Negative pole, including active material；And electrolyte.Above-mentioned lithium secondary battery includes positive pole, negative pole and divides
From film, between above-mentioned positive pole and negative pole, the seperation film for being insulated to above-mentioned motor is well-known TPO
Seperation film, it is possible to use form load seperation film of organic inorganic composite layers etc. in said polyolefins base material, and be not particularly limited
Above-mentioned seperation film.
The present invention can provide the medium-and-large-sized battery module making multiple above-mentioned lithium secondary battery electrical connections or battery pack.In above-mentioned
Large-sized battery module or battery pack can be used for including heavy machine tool (Power Tool), electric vehicle (EV, Electric
Vehicle), hybrid electric vehicle (HEV, Hybrid Electric Vehicle) and plug-in hybrid-power automobile
The electric vehicle of (PHEV, Plug-in Hybrid Electric Vehicle), electric truck, electric commercial vehicle or electric power storage
Deposit the medium-and-large-sized device power supply (DPS) with one or more of system.
Hereinafter, in order to help understand the present invention, preferred embodiment is proposed.But, below example is only used for more holding
Change places and understand the present invention, the invention is not limited in following examples.
Embodiment
Embodiment 1
Under the conditions of Li/Me (=Ni+Co+Mn)=1.03～1.05, mix Ni0.5Co0.2Mn0.3(OH)2Precursor (manufactures
Business：BOUMPLE) and Li2CO3(manufacturer：Lockwood) after, using the RHK continuous oven for 40m for the length, under air ambient,
Carry out being heat-treated 10 hours to prepare Li at a temperature of 910 DEG C～930 DEG CxNi0.5Co0.2Mn0.3O2.Pulverized using winnowing machine
LixNi0.5Co0.2Mn0.3O2Afterwards, filtered (sieve) to prepare lithium-containing compound L-1 by 400mesh.
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
1000ppm)、B2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=300ppm) and n-SiO2The aqueous solution (manufactures
Business：Aladdin) (n-SiO2Concentration (w/w)=500ppm) after, to prepare at surface than mixing mentioned component by identical weight
Reason solution S -1.
Afterwards, it is slowly added lithium-containing compound L-1 using the device shown in Fig. 1 to surface processing solution S-1 and stir, directly
To surface processing solution S-1 and lithium-containing compound L-1 weight than for 1：2, after completing to add, carry out about 1 hour
Add stirring.Afterwards, mixing and the drying of 3～5 hours have been carried out at a temperature of 100 DEG C.Afterwards, at a temperature of 500 DEG C, enter
After the additional heat treatment gone more for 5 hours, carry out classification to prepare positive electrode for lithium secondary battery work eventually through 400mesh
Property material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 2
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
1000ppm)、B2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=500ppm) and n-SiO2The aqueous solution (manufactures
Business：Aladdin) (n-SiO2Concentration (w/w)=300ppm) after, to prepare at surface than mixing mentioned component by identical weight
Reason solution S -2.
Afterwards, it is slowly added lithium-containing compound L-1 using device as shown in Figure 1 to surface processing solution S-2 and carry out
Stirring, until the weight ratio of surface processing solution S-2 and lithium-containing compound L-1 is for 1：2, after completing to add, carry out about 1
The additional stirring of hour.Afterwards, mixing and the drying of 4～6 hours have been carried out at a temperature of 100 DEG C.Afterwards, in 300 DEG C of temperature
Under degree, after having carried out the additional heat treatment more for 5 hours, carry out classification to prepare lithium secondary battery eventually through 400mesh
Use positive active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 3
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
500ppm)、B2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=500ppm) and n-SiO2The aqueous solution (manufactures
Business：Aladdin) (n-SiO2Concentration (w/w)=500ppm) after, to prepare at surface than mixing mentioned component by identical weight
Reason solution S -3.
Afterwards, it is slowly added lithium-containing compound L-1 using device as shown in Figure 1 to surface processing solution S-3 and carry out
Stirring, until the weight ratio of surface processing solution S-3 and lithium-containing compound L-1 is for 1：2, after completing to add, carry out about 1
The additional stirring of hour.Afterwards, mixing and the drying of 3～5 hours have been carried out at a temperature of 100 DEG C.Afterwards, in 700 DEG C of temperature
Under degree, after having carried out the additional heat treatment more for 5 hours, carry out classification to prepare lithium secondary battery eventually through 400mesh
Use positive active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 4
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
500ppm)、B2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=100ppm) and n-SiO2The aqueous solution (manufactures
Business：Aladdin) (n-SiO2Concentration (w/w)=500ppm) after, to prepare at surface than mixing mentioned component by identical weight
Reason solution S -4.
Afterwards, it is slowly added lithium-containing compound L-1 using device as shown in Figure 2 to surface processing solution S-4 and carry out
Stirring, until the weight ratio of surface processing solution S-4 and lithium-containing compound L-1 is for 1：2, after completing to add, carry out about 1
The additional stirring of hour.Afterwards, mixing and the drying of 3～5 hours have been carried out at a temperature of 100 DEG C.Afterwards, in 500 DEG C of temperature
Under degree, after having carried out the additional heat treatment more for 5 hours, carry out classification to prepare lithium secondary battery eventually through 400mesh
With positive active material, and the scanning electron of the above-mentioned positive active material for lithium secondary battery of (a) observation shown partially in Fig. 3
Microphotograph.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 5
Under the conditions of Li/Me (=Ni+Co+Mn)=1.03～1.05, mix Ni0.6Co0.2Mn0.2(OH)2Precursor (manufactures
Business：BOUMPLE) and Li2CO3(manufacturer：Lockwood) after, using the RHK continuous oven for 40m for the length, under air ambient,
Carry out being heat-treated 10 hours to prepare Li at a temperature of 860 DEG C～880 DEG CxNi0.6Co0.2Mn0.2O2.Pulverized using winnowing machine
LixNi0.6Co0.2Mn0.2O2Afterwards, filtered (sieve) to prepare lithium-containing compound L-2 by 400mesh.
Afterwards, in addition to replacing lithium-containing compound L-1 to use lithium-containing compound L-2, by same as Example 1
Method prepares positive active material for lithium secondary battery, and the above-mentioned positive electrode for lithium secondary battery of (b) observation shown partially in Fig. 3
The electron scanning micrograph of active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 6
In addition to replacing lithium-containing compound L-1 to use lithium-containing compound L-2, by method same as Example 2
Prepare positive active material for lithium secondary battery, and (c) observation shown partially above-mentioned positive electrode for lithium secondary battery activity in Fig. 3
The electron scanning micrograph of material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 7
In addition to replacing lithium-containing compound L-1 to use the lithium-containing compound L-2 of preparation in embodiment 5, finally lead to
Cross method same as Example 3 and prepare positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 8
In addition to replacing lithium-containing compound L-1 to use the lithium-containing compound L-2 of preparation in embodiment 5, eventually through
Method same as Example 4 prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 9
Under the conditions of Li/Me (=Ni+Co+Mn)=1.03～1.05, mix Ni0.7Co0.15Mn0.15(OH)2Precursor (manufactures
Business：BOUMPLE) and Li2CO3(manufacturer：Lockwood) after, using the RHK continuous oven for 40m for the length, under air ambient,
Carry out being heat-treated 10 hours to prepare Li at a temperature of 780 DEG C～800 DEG CxNi0.7Co0.2Mn0.15O2.Carrying out powder using winnowing machine
Broken LixNi0.7Co0.15Mn0.15O2Afterwards, filtered (sieve) to prepare lithium-containing compound L-3 by 400mesh.
Afterwards, except replace lithium-containing compound L-1 and in addition to using lithium-containing compound L-3, eventually through with embodiment 1 phase
Same method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 10
In addition to replacing lithium-containing compound L-1 to use the lithium-containing compound L-3 of preparation in embodiment 9, finally lead to
Cross method same as Example 2 and prepare positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 11
In addition to replacing lithium-containing compound L-1 to use the lithium-containing compound L-3 of preparation in embodiment 9, finally lead to
Cross method same as Example 3 and prepare positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 12
In addition to replacing lithium-containing compound L-1 to use the lithium-containing compound L-3 of preparation in embodiment 9, finally lead to
Cross method same as Example 4 and prepare positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 13
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
1000ppm)、B2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=3000ppm) after, by identical weight ratio
Mix mentioned component to prepare surface processing solution S-5.
Afterwards, except replace surface processing solution S-1 and in addition to using surface processing solution S-5, eventually through with enforcement
Example 1 identical method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 14
Preparing Al (OH) respectively3The aqueous solution (manufacturer：This promise chemistry, China) (Al (OH)3Concentration (w/w)=
500ppm) and n-SiO2The aqueous solution (manufacturer：Aladdin) (n-SiO2Concentration (w/w)=300ppm) after, by identical weight ratio
Mix mentioned component to prepare surface processing solution S-6.
Afterwards, except replace surface processing solution S-2 and in addition to using surface processing solution S-6, eventually through with enforcement
Example 2 identical method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 15
Preparing B respectively2O3The aqueous solution (manufacturer：Pure chemistry) (B2O3Concentration (w/w)=500ppm) and n-SiO2Water
Solution (manufacturer：Aladdin) (n-SiO2Concentration (w/w)=500ppm) after, to make than mixing mentioned component by identical weight
Standby surface processing solution S-7.
Afterwards, except replace surface processing solution S-2 and in addition to using surface processing solution S-7, eventually through with enforcement
Example 3 identical method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Embodiment 16
Under conditions of Li/Me (=Ni+Co+Mn)=1.03, mix Ni0.8Co0.1Mn0.1(OH)2Precursor (manufacturer：Nation
General) and Li2CO3(manufacturer：Lockwood) after, using the RHK continuous oven for 40m for the length, under air ambient, at 760 DEG C
At a temperature of carry out being heat-treated 10 hours to prepare LixNi0.8Co0.1Mn0.1O2.Pulverized using winnowing machine
LixNi0.8Co0.1Mn0.1O2Afterwards, filtered (sieve) to prepare lithium-containing compound L-4 by 400mesh.
Afterwards, except replacing lithium-containing compound L-1 to be added using lithium-containing compound L-4 and at a temperature of 400 DEG C
Outside heat treatment about 5 hours, prepare positive active material for lithium secondary battery eventually through method same as Example 1.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=5 μm～7 μm.
Embodiment 17
Except using the Al of 1000ppm as application substance2O3And the ZrO of 1000ppm2To replace
LixNi0.8Co0.1Mn0.1O2Powder prepares LixNi0.8Co0.1Mn0.08Al0.01Zr0.01O2Outside, eventually through with embodiment 16 phase
Same method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=5 μm～7 μm.
Embodiment 18
Except using the Al of 2000ppm as application substance2O3And the ZrO of 1000ppm2To replace
LixNi0.8Co0.1Mn0.1O2Powder prepares LixNi0.8Co0.1Mn0.07Al0.02Zr0.01O2Outside, eventually through with embodiment 16 phase
Same method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=5 μm～7 μm.
Embodiment 19
Except using the Al of 3000ppm as application substance2O3And the ZrO of 1000ppm2To replace
LixNi0.8Co0.1Mn0.1O2Powder prepares LixNi0.8Co0.1Mn0.06Al0.03Zr0.01O2Outside, eventually through with embodiment 16 phase
Same method prepares positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=5 μm～7 μm.
Comparative example 1
The lithium-containing compound prepared in embodiment 1 L-1 to be used as positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 2
The lithium-containing compound L-2 of preparation in embodiment 5 to be used as positive active material for lithium secondary battery, and
Electron scanning micrograph in the above-mentioned positive active material for lithium secondary battery of (d) of Fig. 3 observation shown partially.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 3
The lithium-containing compound L-3 of preparation in embodiment 9 to be used as positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 4
Business is prepared by lithium-containing compound L4 and uses LiCoO2, to prepare B as surface processing solution S-72O3The aqueous solution
(manufacturer：Pure chemistry) (B2O3Concentration (w/w)=300ppm).
Afterwards, it is slowly added lithium-containing compound L-4 using device as shown in Figure 1 to surface processing solution S-7 and carry out
Stirring, until the weight ratio of surface processing solution S-7 and lithium-containing compound L-4 reaches 1：2, after completing to add, add and stir
Mix more 1 hour.Afterwards, mixed at a temperature of 100 DEG C and be dried about 3～6 hours afterwards, carried out eventually through 40mesh
It is classified and to prepare positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 5
In addition to being mixed and be dried at a temperature of 300 DEG C, prepare lithium two eventually through with comparative example 4 identical method
Primary cell positive active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 6
In addition to being mixed and be dried at a temperature of 500 DEG C, prepare lithium two eventually through with comparative example 4 identical method
Primary cell positive active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 7
In addition to being mixed and be dried at a temperature of 700 DEG C, prepare lithium two eventually through with comparative example 4 identical method
Primary cell positive active material.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 8
The UM preparing in Umicore Company NCM111 product to be prepared as positive active material for lithium secondary battery.
The result positive active material of final preparation being analyzed by particle size analyzer, D50=11 μm～13 μm.
Comparative example 9
The UM preparing in Umicore Company NCM523 product to be prepared as positive active material for lithium secondary battery.
The result final other positive active material being analyzed by particle size analyzer, D50=11 μm～13 μm.
Table 1
Experimental example
(1) the X diffraction crystalline texture of positive active material
X diffraction crystal structure analysis are carried out to the positive active material of preparation final in embodiment 2 and comparative example 1, and
Figure 4 illustrates the above results.
As shown in figure 4, as embodiment 2, in the case of being surface-treated by multiple compounds, with such as comparative example 1
The situation that shown not carrying out is surface-treated is compared, and can confirm that generation low-angle is mobile (low angle shift).Because carrying out table
Face is processed, and increases lattice paprmeter and increase, thus there is above-mentioned phenomenon.
Especially, in the case of embodiment 2, after being surface-treated, carry out surface coating by adding heat treatment
(surface doping), therefore increases the lattice paprmeter of the unit lattice (unit cell) of crystalline texture, sends out thus can confirm that
Give birth to low-angle movement.
(2) the life characteristic evaluation of button cell
In the positive active material of final preparation in embodiment and comparative example, conductive material：The weight ratio of binding agent is
95：2.5：2.5, after using nmp solution to prepare anode active material slurry, with the preparation of pole plate density 3.3g/cc condition
Anode plate, using Li metal negative electrode and EC/DMC/DEC [1/1/1]+1MLiPF6Button to be prepared in the drying chamber by electrolyte
Battery.Afterwards, implement initial charge electric discharge under 0.1C/0.1C charge-discharge conditions.
After implementing initial charge electric discharge, at a temperature of 25 DEG C, at 4.5～3.0V 1C/1C (or 0.5C/0.5C)
Implement charging and discharging under charge-discharge conditions the normal temperature life characteristic of button cell is evaluated, and in Fig. 5 a～Fig. 5 d
The above results are shown.
And, after implementing initial charge electric discharge, at a temperature of 45 DEG C, in 4.5～3.0V1C/1C (or 0.5C/
0.5C) under charge-discharge conditions implement charging and discharging the life characteristics at high temperature of button cell is evaluated, and Fig. 6 a～
The above results shown in Fig. 6 e.
As shown in Fig. 5 a～Fig. 5 d and Fig. 6 a～Fig. 6 e, such as embodiment, be surface-treated by multiple compounds
In the case of, the situation that not the carrying out of such as comparative example is surface-treated is compared, and can confirm that normal temperature and the life characteristics at high temperature of button cell
Outstanding.
Specifically, compared with comparative example 1, in the case of embodiment 1～3 and embodiment 13, circulating it through 60 times
Afterwards, can confirm that button cell capacity retention improves about 2%, thus can confirm that the outstanding of the normal temperature life characteristic of button cell
(reference picture 5a and Fig. 5 b).
And, compared with comparative example 1, in the case of embodiment 1～3 and embodiment 13, through 80 times circulate after,
Can confirm that the capacity retention of button cell improves about 4%, compared with comparative example 1, in the case of embodiment 13, through 70
After secondary circulation, can confirm that the capacity retention of button cell improves about 0.5%, thus can confirm that the high temperature service life of button cell
Characteristic outstanding (reference picture 6a and Fig. 6 b).
And, compared with embodiment 16, in the case of embodiment 18, after 50 times circulate, can confirm that button
The capacity retention of battery improves about 4%, thus can confirm that outstanding (Figure 10) of the life characteristics at high temperature of button cell.This be because
It is to lithium-containing compound coating element-specific it is preferable that carrying out the result of composite coating.And, in embodiment 16 and embodiment
In the case of 18, in the particle of positive active material is distributed, when by a diameter of for 50% mass accumulation particle size distribution D50
When, corresponding with the particulate that D50 is 5 μm～7 μm, in the case of using above-mentioned particulate, can confirm that the high temperature longevity of button cell
Life characteristic is outstanding.
(3) the life characteristic evaluation of fuel cell
In the positive active material of final preparation in embodiment 2, embodiment 13 and comparative example 1, conductive material：Binding agent
Weight than for 92：5：3, after using nmp solution to prepare anode active material slurry, with pole plate density 3.3～3.4g/
Cc condition prepares anode plate, using Li metal negative electrode and EC/DMC/DEC [1/1/1]+1M LiPF6Electrolyte is angular to prepare
Fuel cell.Afterwards, implement initial charge electric discharge under 0.1C/0.1C charge-discharge conditions.
After implementing initial charge electric discharge, at a temperature of 25 DEG C, under 4.2～3.0V 1C/1C charge-discharge conditions
Implement charging and discharging the normal temperature life characteristic of fuel cell is evaluated, and the above results shown in Fig. 5 e.
And, after implementing initial charge electric discharge, at a temperature of 45 DEG C, in 4.2～3.0V1C/1C (or 0.5C/
0.5C) implement charging and discharging under charge-discharge conditions the life characteristics at high temperature of fuel cell is evaluated, and in Fig. 6 f
The above results are shown.
As shown in Fig. 5 e and Fig. 6 f, as shown in embodiment 2, embodiment 13, it is being surface-treated by multiple compounds
In the case of, compared with situation about being surface-treated with not the carrying out as shown in comparative example 1, can confirm that normal temperature and the high temperature of fuel cell
Life characteristic outstanding.
(4) evaluation of the C-rate change based on button cell
Pass through said method in (2), using preparation final in embodiment 10 and comparative example 3 positive active material Lai
Prepare button cell.Afterwards, under 0.1C/0.1C charge-discharge conditions, implement initial charge electric discharge after, by 0.2C,
The order of 0.33C, 0.5C, 1.0C, 3.0C and 5.0C changes C-rate and the capacity retention of button cell is evaluated, and
Figure 7 illustrates the above results.
As shown in fig. 7, compared with comparative example 3, in the case of example 10, under conditions of 3.0C and 5.0C, also may be used
Confirm that button cell has high capacity retention.
(5) Evaluation of Thermal Stability of button cell (coin cell)
By the method described in (2), using preparation final in embodiment 2, embodiment 13～15 and comparative example 1
Positive active material is preparing button cell.Afterwards, release, in hothouse, the button cell being charged by 4.3V to separate
Pole plate.In detached pole plate, about extract 10mg about be coated on positive active material on aluminium foil and using 910DSC (TA instrument
Device Products) implementing dsc analysis.Dsc analysis are under air ambient, between 25 DEG C～300 DEG C within the temperature range of
Scanning is implemented with the programming rate of 3 DEG C/min.Figure 8 illustrates dsc analysis result.
As shown in figure 8, the hot-fluid compared with comparative example 1, in the case of embodiment 2, embodiment 13～15, based on temperature
Amount peak value is not high, thus can confirm that the outstanding of thermostability.
(6) the expansion characteristics evaluation based on fuel cell
By the method described in (2), finally make using in embodiment 2 and comparative example 1, comparative example 8, comparative example 9
Standby positive active material is preparing fuel cell.Afterwards, 7 are placed at a temperature of 60 DEG C afterwards, in this case, mutually
Compare the phenomenon of fuel cell high-temperature expansion (hotswelling), temperature is reduced to normal temperature (25 DEG C) to be compared to each other fuel
The phenomenon of battery low-temperature expansion (cold swelling), and figure 9 illustrates the above results.
As shown in figure 9, compared with comparative example 1, comparative example 8, comparative example 9, in the case of embodiment 2, can confirm that expansion
The raising of characteristic.Especially, in the case of embodiment 2, in the state of placing fuel cell at 60 DEG C, can confirm that there is brilliance
High-temperature expansion effect.
(7) evaluation of the C-rate change based on fuel cell
By the method described in (2), using the positive electrode active material of preparation final in embodiment 18 and embodiment 19
Matter is preparing fuel cell.Afterwards, under 0.1C/0.1C charge-discharge conditions, after implementing initial charge electric discharge, by 2C and
The order of 4C changes C-rate and the high output characteristic of fuel cell is evaluated, and figure 11 illustrates the above results.
As shown in figure 11, compared with embodiment 18, in the case of embodiment 19, can confirm that and be susceptible to electric discharge phenomena.
Compared with Low C-rate, can confirm that the discharge capacity in High C-rate is big.Therefore, in order to ensure high output characteristic, need
Adjust the amount of the element-specific to lithium-containing compound coating.
And, in the case of embodiment 18 and embodiment 19, in the particle of positive active material is distributed, when by 50%
During a diameter of D50 of mass accumulation particle size distribution, corresponding with the particulate that D50 is 5 μm～7 μm, using above-mentioned particulate
In the case of, can confirm that the high output characteristic of fuel cell is outstanding.
The explanation of the invention described above is used for illustrating, and general technical staff of the technical field of the invention is appreciated that constant
Other concrete forms can be easily deformed in the case of the technological thought of the more present invention or essential feature.Therefore, above description
Embodiment is all exemplary embodiments in all respects, is not intended to limit the present invention.
Claims (15)
1. a kind of positive active material for lithium secondary battery it is characterised in that
Comprise：
Lithium-containing compound；And
Surface-treated layer, is formed on above-mentioned lithium-containing compound,
Above-mentioned surface-treated layer comprises selected from Al (OH)3, boride alloy and compound containing Si composition group in two or more
Compound.
2. positive active material for lithium secondary battery according to claim 1 is it is characterised in that above-mentioned lithium-containing compound bag
Containing in the group selected from lithium, nickel, cobalt, manganese class compound, lithium-nickel-cobalt-aluminium class compound and lithium-cobalt class compound composition
Plant above compound.
3. positive active material for lithium secondary battery according to claim 1 is it is characterised in that above-mentioned lithium-containing compound is
The lithium, nickel, cobalt, manganese class compound being represented with following chemical formula 1：
Chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In above-mentioned formula, 0.95≤x≤1.1,0.05≤y≤0.2,0.05≤z≤0.3,0≤a≤0.04, M be selected from Mg,
One or more of group of Ti, Al and Zr composition, A is in the group selected from O, F, S and P composition.
4. positive active material for lithium secondary battery according to claim 1 it is characterised in that above-mentioned surface-treated layer or
Person comprises Al (OH)3, boride alloy and compound containing Si, or comprise Al (OH)3And boride alloy, or comprise Al (OH)3
And compound containing Si, or comprise boride alloy and compound containing Si.
5. positive active material for lithium secondary battery according to claim 1 is it is characterised in that in above-mentioned surface-treated layer
Comprise Al (OH)3, in the case of boride alloy and compound containing Si, with respect to the Al (OH) of 100 weight portions3, comprise 20 weight
Part is to the boride alloy of 100 weight portions and the compound containing Si of 30 weight portions to 100 weight portions.
6. positive active material for lithium secondary battery according to claim 1 is it is characterised in that in above-mentioned positive electrode active material
In the particle distribution of matter, as a diameter of D50 of 50% mass accumulation particle size distribution, D50 is 5 μm～7 μm.
7. a kind of preparation method of positive active material for lithium secondary battery is it is characterised in that include：
Step a, prepares lithium-containing compound；
Step b, preparation comprises selected from Al (OH)3In the group of solution, boride alloy solution and the composition of compound solution containing Si
The surface processing solution of two or more solution；And
Step c, the lithium-containing compound preparing is added to the surface treatment preparing in above-mentioned steps b molten in above-mentioned steps a
After liquid, mixed and be dried.
8. the preparation method of positive active material for lithium secondary battery according to claim 7 is it is characterised in that above-mentioned
In step b, Al (OH)3Solution, boride alloy solution or compound solution containing Si using water or less than 95% ethanol as solvent
To use.
9. the preparation method of positive active material for lithium secondary battery according to claim 7 is it is characterised in that above-mentioned
In step b, Al (OH)3The concentration of each solute in solution, boride alloy solution or compound solution containing Si is for 1ppm extremely
1000ppm.
10. the preparation method of positive active material for lithium secondary battery according to claim 7 is it is characterised in that upper
State in step c, the weight of surface processing solution and lithium-containing compound is than for 0.5：1 to 1：3.
The preparation method of 11. positive active material for lithium secondary battery according to claim 7 is it is characterised in that upper
State in step c, execution simultaneously mixes and is dried.
The preparation method of 12. positive active material for lithium secondary battery according to claim 7 is it is characterised in that upper
State in step c, mix and be dried execution 1 hour to 10 hours at a temperature of 50 DEG C to 150 DEG C.
The preparation method of 13. positive active material for lithium secondary battery according to claim 7 is it is characterised in that also wrap
Include step d, carry out adding heat treatment at a temperature of higher than the baking temperature in above-mentioned steps c.
The preparation method of 14. positive active material for lithium secondary battery according to claim 13 is it is characterised in that above-mentioned
Add heat treatment to execute 1 hour to 10 hours at a temperature of 100 DEG C to 700 DEG C.
A kind of 15. lithium secondary batteries are it is characterised in that just comprise secondary lithium batteries any one of claim 1 to 6
Pole active material.
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| KR1020160086175A KR101871919B1 (en) | 2015-07-30 | 2016-07-07 | Positive active material for lithium secondary battery and method of preparing the same and lithium secondary battery comprising the same |
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| CN1466235A (en) * | 2001-10-17 | 2004-01-07 | ����Sdi��ʽ���� | Method for producing active material for lightium secondary battery |
| US20150207184A1 (en) * | 2012-07-26 | 2015-07-23 | Schott Ag | Additive for electrochemical energy storages and electrochemical energy storage |
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