CN107359342A - Lithium phosphate ferromanganese system particle, lithium phosphate ferromanganese system powder and preparation method thereof - Google Patents
Lithium phosphate ferromanganese system particle, lithium phosphate ferromanganese system powder and preparation method thereof Download PDFInfo
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Abstract
A kind of lithium phosphate ferromanganese system powder, including multiple lithium phosphate ferromanganese system particles.Each lithium phosphate ferromanganese system particle includes core portion and shell portion.Core portion includes multiple the first lithium phosphate manganese Fe nanomaterials for being combined together and having the first average grain diameter.Shell portion includes multiple the second lithium phosphate manganese Fe nanomaterials for being combined together and having the second average grain diameter, and the second average grain diameter is more than the first average grain diameter.300 to 450 DEG C of preliminary sintering processes, the intermediate sintering processing more than 450 to 600 DEG C, and the last sintering processes more than 600 to 800 DEG C are sequentially carried out, above-mentioned lithium phosphate ferromanganese system powder can be made.Cathode material with lithium phosphate ferromanganese system's powder as lithium battery, can make lithium battery have high energy density, and good high temperature charge and discharge cycles stability and heat endurance concurrently.
Description
Technical field
The present invention is to be related to a kind of be applied to as lithium phosphate ferromanganese system's powder of cathode materials for lithium battery and its preparation side
Method, more particularly to a kind of lithium phosphate ferromanganese system powder of the lithium phosphate ferromanganese system particle including multiple nucleocapsid shapes, and it is described
Lithium phosphate ferromanganese system powder preparation method.
Background technology
It can not yet reach currently used for the lithium phosphate ferromanganese system powder as cathode materials for lithium battery (or positive electrode)
The stage of shiploads of merchandise, the mainly electrical conductivity because of lithium phosphate ferromanganese system powder in itself are relatively low, cause how to take into account lithium battery
High-energy-density and heat endurance the problem of turning into most critical.The technology of early stage is by preparing the phosphorus with compared with low specific surface area
Sour lithium ferromanganese system powder, the average grain diameter of its primary particle (primary particle) are approximately more than 300nm, can cause lithium battery
Heat endurance and charge and discharge cycles stability accord with the demands of the market, but because lithium phosphate ferromanganese system powder essence electric conductivity is inclined
It is low, so the performance of discharge capability of the lithium battery in energy density and high current is still undesirable.Therefore in order to improve phosphoric acid
The electrochemical properties of lithium ferromanganese system powder, for a small number of technologies by improving synthetic method, the average grain diameter for preparing primary particle is small
In 100nm lithium phosphate ferromanganese system powder, by the distance for shortening the powder electronics conduction of lithium phosphate ferromanganese system, lithium phosphate manganese is lifted
The electric conductivity of iron system powder, though this mode can effectively improve the capacitance and discharge performance of lithium battery, the energy for reaching higher is close
Degree, but cause lithium battery with respect to the specific surface area that can increase lithium phosphate ferromanganese system powder after lithium phosphate ferromanganese system particle nanosizing
The increase of negative electrode and electrolyte response area, charge and discharge cycles stability and heat endurance during the high temperature of lithium battery is deteriorated.
The content of the invention
The first object of the present invention is to provide a kind of lithium phosphate ferromanganese system being applied to as cathode materials for lithium battery
Grain.
Lithium phosphate ferromanganese system particle of the present invention, suitable for the cathode material as lithium battery, the lithium phosphate ferromanganese system
Grain includes：
One core portion, including multiple first lithium phosphate manganese Fe nanomaterials, the first lithium phosphate manganese Fe nanomaterial
It is bound together and there is one first average grain diameter；And
One shell portion, the core portion is coated, and including multiple second lithium phosphate manganese Fe nanomaterials, second lithium phosphate
Manganese Fe nanomaterial is bound together and has one second average grain diameter, and second average grain diameter is more than described first
Average grain diameter.
Lithium phosphate ferromanganese system particle of the present invention, the model of the first average grain diameter of the first lithium phosphate manganese Fe nanomaterial
Enclose for 30 to 150nm.
Lithium phosphate ferromanganese system particle of the present invention, the model of the second average grain diameter of the second lithium phosphate manganese Fe nanomaterial
Enclose for 150 to 400nm.
Lithium phosphate ferromanganese system particle of the present invention, the chemistry meter of the first lithium phosphate manganese Fe nanomaterial in the core portion
Amount composition is identical with the stoichiometric composition of the second lithium phosphate manganese Fe nanomaterial in the shell portion.
Lithium phosphate ferromanganese system particle of the present invention, the first lithium phosphate manganese Fe nanomaterial and second lithium phosphate manganese
The stoichiometric composition of Fe nanomaterial is LixMn1-y-zFeyMzPO4, and 0.9≤x≤1.2,0.1≤y≤0.4,0≤z≤
0.1, and the condition of 0.1≤y+z≤0.4, wherein, M is selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminium or above-mentioned
One combination.
Lithium phosphate ferromanganese system particle of the present invention, the first lithium phosphate manganese Fe nanomaterial is one by sinter bonded
Rise, and the second lithium phosphate manganese Fe nanomaterial be by sinter bonded together.
The second object of the present invention is to provide a kind of lithium phosphate ferromanganese system powder being applied to as cathode materials for lithium battery
Body.
Lithium phosphate ferromanganese system powder of the present invention, including multiple lithium phosphate ferromanganese system as described above particles.
Lithium phosphate ferromanganese system powder of the present invention, the average particle size range of the lithium phosphate ferromanganese system particle is 0.6 to 20 μm.
Lithium phosphate ferromanganese system powder of the present invention, the scope of specific surface area is 5 to 30m2/g。
Lithium phosphate ferromanganese system powder of the present invention, tap density scope are more than 0.5g/cm3。
The third object of the present invention is to provide a kind of lithium phosphate ferromanganese system powder being applied to as cathode materials for lithium battery
The preparation method of body.
Lithium phosphate ferromanganese system raw powder's production technology of the present invention, is comprised the steps of：
(A) admixture containing a lithium source, a manganese source, a source of iron and a phosphorus source is provided；
(B) admixture is ground and is granulated to form a granulation mixture；
(C) granulation mixture is subjected to a preliminary sintering processes to form a pre-formed articles, wherein, the preliminary burning
The temperature range of knot processing is 300 to 450 DEG C；
(D) pre-formed articles are subjected to an intermediate sintering processing to form the pre-formed articles once intermediate sintering, wherein,
The temperature range of the intermediate sintering processing is more than 450 to 600 DEG C；And
(E) pre-formed articles through intermediate sintering are subjected to a last sintering processes to form lithium phosphate ferromanganese system powder
Body, wherein, the temperature range of the last sintering processes is more than 600 to 800 DEG C.
Lithium phosphate ferromanganese system raw powder's production technology of the present invention, the admixture also containing one selected from magnesium, calcium, strontium, cobalt,
Titanium, zirconium, nickel, chromium, zinc, aluminium or the doping metals source of above-mentioned one combination.
The beneficial effects of the present invention are：The preparation method by the step (A) to (E) be made include it is multiple generally into
The lithium phosphate ferromanganese system powder of the lithium phosphate ferromanganese system particle of nucleocapsid shape, and the second of each its shell portion of lithium phosphate ferromanganese system particle
Second average grain diameter of lithium phosphate manganese Fe nanomaterial is more than the first flat of the first lithium phosphate manganese Fe nanomaterial in core portion
Equal particle diameter.When cathode material of the lithium phosphate ferromanganese system powder as lithium battery, the energy density of lithium battery is enabled to
High, heat endurance height, and the charge and discharge cycles good stability in high temperature.
Brief description of the drawings
Fig. 1 is the photo of the sweep electron microscope of the lithium phosphate ferromanganese system particle of embodiments of the invention 1；
Fig. 2 is the partial enlarged drawing of the photo of the sweep electron microscope of the embodiment 1；
Fig. 3 is the photo of the sweep electron microscope of the lithium phosphate ferromanganese system particle of comparative example 1；
Fig. 4 is the partial enlarged drawing of the photo of the sweep electron microscope of the lithium phosphate ferromanganese system particle of comparative example 1；
Fig. 5 is the photo of the sweep electron microscope of the lithium phosphate ferromanganese system particle of comparative example 2；
Fig. 6 is the partial enlarged drawing of the photo of the sweep electron microscope of the lithium phosphate ferromanganese system particle of comparative example 2；
Fig. 7 be embodiment 1, comparative example 1 and 2 the button type lithium batteries of CR 2032 0.1C current charge-discharge electrical testings
(Capacity) datagram；
Fig. 8 is that embodiment 1, the button type lithium batteries of CR 2032 of comparative example 1 and 2 are put in 0.1C, 1.0C, 5.0C, 10.0C
The datagram of electric testing current (C-rate)；
Fig. 9 be embodiment 1, comparative example 1 and 2 the button type lithium batteries of CR 2032 55 DEG C of high temperature circulations test (Cycle
Life datagram)；And
Figure 10 be embodiment 1, comparative example 1 and 2 the button type lithium batteries of CR 2032 heat analysis test (Safety) number
According to figure.
Embodiment
Present invention is described in detail below：
Herein, its scope of the term of " lithium battery " covers：For " the lithium of " one-shot battery (primary battery) "
Battery (lithium battery) ", the and " lithium ion battery for " secondary cell (secondary battery) "
(lithium-ion battery)」.Lithium phosphate ferromanganese system powder of the present invention can be as the cathode material or " lithium of " lithium battery "
The cathode material of ion battery ", especially apply the cathode material as " lithium ion battery ".
＜ lithium phosphate ferromanganese system particle, lithium phosphate ferromanganese system powder ＞
It is preferred that the average grain of the first of the first lithium phosphate manganese Fe nanomaterial of the lithium phosphate ferromanganese system particle
The scope in footpath is 30 to 150nm, and the TELESPEED and matter that can more lift the lithium phosphate ferromanganese system powder pass speed.
It is preferred that the average grain of the second of the second lithium phosphate manganese Fe nanomaterial of the lithium phosphate ferromanganese system particle
The scope in footpath is 150 to 400nm, can more reduce the specific surface area of the lithium phosphate ferromanganese system powder.
It is preferred that in the lithium phosphate ferromanganese system particle, the first lithium phosphate manganese Fe nanomaterial in the core portion
Stoichiometric composition it is identical with the stoichiometric composition of the second lithium phosphate manganese Fe nanomaterial in the shell portion.More preferably
Ground, the stoichiometric composition of the first lithium phosphate manganese Fe nanomaterial and the second lithium phosphate manganese Fe nanomaterial are
LixMn1-y-zFeyMzPO4, and the condition of 0.9≤x≤1.2,0.1≤y≤0.4,0≤z≤0.1, and 0.1≤y+z≤0.4, its
In, M is to be selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminium or an above-mentioned combination.
It is preferred that in the lithium phosphate ferromanganese system particle, the first lithium phosphate manganese Fe nanomaterial is to pass through sintering
Be combined together, and the second lithium phosphate manganese Fe nanomaterial be by sinter bonded together.
It is preferred that in the lithium phosphate ferromanganese system powder, the average particle size range of the lithium phosphate ferromanganese system particle is 0.6
To 20 μm.
It is preferred that the scope of the specific surface area of the lithium phosphate ferromanganese system powder is 5 to 30m2/g。
It is preferred that the tap density scope of the lithium phosphate ferromanganese system powder is more than 0.5g/cm3。
＜ lithium phosphate ferromanganese system raw powder's production technology ＞
The lithium phosphate ferromanganese system raw powder's production technology comprises the steps of：Will contain the lithium source, manganese source, source of iron and
The admixture of phosphorus source is ground and granulation forms the granulation mixture；The granulation mixture is sequentially tentatively burnt
Knot processing, intermediate sintering processing and last sintering processes.
It is preferred that phosphorus source is water miscible.The species of phosphorus source be such as, but not limited to phosphoric acid, ammonium dihydrogen phosphate,
Sodium phosphate or sodium dihydrogen phosphate etc., above-mentioned phosphorus source can the individually a kind of or a variety of uses of mixing.More preferably, phosphorus source is phosphoric acid.
The species of the manganese source is such as, but not limited to manganese oxide, manganese oxalate, manganese carbonate, manganese sulfate or manganese acetate etc., above-mentioned
Manganese source can the individually a kind of or a variety of uses of mixing.It is preferred that the manganese source is manganese oxide.Rubbed using the usage amount of phosphorus source as 1
You, the usage amount scope of the manganese source is 0.6 to 0.9 mole.
The species of the source of iron is such as, but not limited to ferric oxalate, iron oxide, pure iron, ferric nitrate or ferric sulfate etc., above-mentioned iron
Source can the individually a kind of or a variety of uses of mixing.It is preferred that the source of iron is ferric oxalate.Using the usage amount of phosphorus source as 1 mole,
The usage amount scope of the source of iron is 0.1 to 0.4 mole.
The species of the lithium source is such as, but not limited to lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate or lithium oxalate etc., on
Stating lithium source can the individually a kind of or a variety of use of mixing.It is preferred that the lithium source is lithium carbonate.Using the usage amount of phosphorus source as 1
Mole, the usage amount scope of the lithium source is 0.9 to 1.2 mole.
It is preferred that the admixture is also selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminium or above-mentioned containing one
The doping metals source of one combination.The doping metals source can improve the structural stability of lithium phosphate ferromanganese system powder.More preferably,
The doping metals source is to be selected from magnesium.Using the usage amount of phosphorus source as 1 mole, the usage amount scope in the doping metals source
For 0.01 to 0.1 mole.
It is preferred that the admixture also contains a carbon source.The effect of the carbon source is as reducing agent.The kind of the carbon source
Class is such as, but not limited to glucose, citric acid, super-P (conductive carbon black) etc., and above-mentioned carbon source individually one or more can use.
The visual demand of admixture optionally contains a solvent.The solvent is such as, but not limited to water.The solvent
Usage amount be not particularly limited, be with the dosage of above-mentioned each source metal and carbon source adjust.
The admixture is formed the mode of the granulation mixture and such as, but not limited to first grind the admixture, then will
The ground admixture is granulated.The mode of the grinding is such as, but not limited to ball-milling method, the condition of the ball-milling method
It is not particularly limited, such as, but not limited to grinds the admixture 1 to 5 hour with 800 to 2400rpm./min speed.Institute
The mode for stating granulation is such as, but not limited to spray granulation, and the condition of the spray granulation is not particularly limited, such as but not
The intake air temperature scope being limited in a sponging granulator is 160 to 210 DEG C, the ground admixture is formed described make
Grain mixture.
The temperature range of the preliminary sintering processes is 300 to 450 DEG C.The processing time of the preliminary sintering processes is for example
But it is not limited to 6 to 12 hours.
The temperature range of the intermediate sintering processing is more than 450 to 600 DEG C.The processing time of the intermediate sintering processing
Such as, but not limited to 2 to 6 hours.
The temperature range of the last sintering processes is more than 600 to 800 DEG C.The processing time of the last sintering processes
Such as, but not limited to 2 to 6 hours.
The present invention will be described further with regard to following examples, however, it should be noted that the embodiment is only to illustrate to say
It is bright, and it is not necessarily to be construed as the limitation that the present invention is implemented.
[embodiment 1]
Under conditions of temperature is more than 30 DEG C, (it is specially by appropriate water, and manganese source (being specially manganese oxide), source of iron
Ferric oxalate), the doping metals source of magnesium (being specially magnesia) and phosphorus source (being specially phosphoric acid) be according to mol ratio 0.8：0.15：
0.05：1.0 mixing, after 1 hour, lithium source (being specially lithium carbonate) mixing is added, and the mol ratio of lithium source and phosphorus source is 1.02：
1.00, appropriate carbon source (being specially glucose) is subsequently added into, obtains an admixture.The admixture is placed in a ball mill
Grinding 4 hours, obtains ground admixture.The ground admixture is spray-dried with a sponging granulator again
(the intake air temperature control of sponging granulator is 200 DEG C), obtains a granulation mixture.The granulation mixture is placed in a clock
In cover stove, under nitrogen atmosphere, it is (small with 450 DEG C of Isothermal sinters 10 that the granulation mixture is first carried out to a preliminary sintering processes
When), form a pre-formed articles.The pre-formed articles are subjected to an intermediate sintering processing (with 600 DEG C of Isothermal sinters 2 hours) again,
Form the pre-formed articles once intermediate sintering.Finally, the pre-formed articles through intermediate sintering are subjected to a last sintering processes
(with 750 DEG C of Isothermal sinters 3 hours), and after naturally cooling to room temperature (25 DEG C), obtain the lithium phosphate ferromanganese system powder of embodiment 1
(specific surface area 18.1m2/ g, tap density 1.21g/cm3)。
With one scan formula electron microscope (manufacturer's model：Hitachi su8000) observation embodiment 1 lithium phosphate ferromanganese system
Powder, Fig. 1 and Fig. 2 photos show, the lithium phosphate ferromanganese system particle in the lithium phosphate ferromanganese system powder of embodiment 1 is included by multiple the
One lithium phosphate manganese Fe nanomaterial (average grain diameter is by 50nm) is combined together the core portion formed, and by multiple second phosphorus
Sour lithium manganese Fe nanomaterial (average grain diameter is by 400nm) is combined together the shell portion formed.And via elementary analysis (analysis
Instrument is PerkinElmer Optima 7000DV), learn the first lithium phosphate manganese Fe nanomaterial and the second lithium phosphate ferromanganese
The stoichiometric composition for being nano-particle is all Li1.02Mn0.8Fe0.15Mg0.05PO4。
[comparative example 1]
Under conditions of temperature is more than 30 DEG C, (it is specially by appropriate water, and manganese source (being specially manganese oxide), source of iron
Ferric oxalate), the doping metals source of magnesium (being specially magnesia) and phosphorus source (being specially phosphoric acid) be according to mol ratio 0.8：0.15：
0.05：1.0 mixing, after 1 hour, lithium source (being specially lithium carbonate) is added, and the mol ratio of lithium source and phosphorus source is 1.02：
1.00, proper amount of carbon source (being specially glucose) is subsequently added into, obtains an admixture.The admixture is placed in a ball mill and ground
Mill 3 hours, obtains ground admixture.The ground mixture is spray-dried with a sponging granulator again
(the intake air temperature control of sponging granulator is 200 DEG C) obtains a granulation mixture.The granulation mixture is placed in bell jar
In stove, under nitrogen atmosphere, by the granulation mixture first with 450 DEG C of Isothermal sinters 8 hours, then it is small with 650 DEG C of Isothermal sinters 6
When, and obtain lithium phosphate ferromanganese system powder (the specific surface area 26.3m of comparative example 1 after naturally cooling to room temperature (25 DEG C)2/ g, shakes
Real density is 1.12g/cm3)。
With one scan formula electron microscope (manufacturer's model：Hitachi su8000) observation comparative example 1 lithium phosphate ferromanganese system
Powder, Fig. 3 and Fig. 4 photos show that the lithium phosphate ferromanganese system particle in the lithium phosphate ferromanganese system powder of comparative example 1 is by multiple phosphoric acid
Lithium manganese Fe nanomaterial (average grain diameter is by 70nm), which is combined together, to be formed.And (analytical instrument is via elementary analysis
PerkinElmer Optima 7000DV), the stoichiometric composition for learning lithium phosphate manganese Fe nanomaterial is
Li1.02Mn0.8Fe0.15Mg0.05PO4。
[comparative example 2]
Under conditions of temperature is more than 30 DEG C, (it is specially by appropriate water, and manganese source (being specially manganese oxide), source of iron
Ferric oxalate), the doping metals source of magnesium (being specially magnesia) and phosphorus source (being specially phosphoric acid) be according to mol ratio 0.8：0.15：
0.05：1.0 mixing, after 1 hour, lithium source (being specially lithium carbonate) is added, and the mol ratio of lithium source and phosphorus source is 1.02：
1.00, proper amount of carbon source (being specially glucose) is subsequently added into, obtains an admixture.The admixture is placed in a ball mill and ground
Mill 2 hours, obtains ground admixture.The ground admixture is spray-dried with a sponging granulator again
(the intake air temperature control of sponging granulator is 200 DEG C) obtains a granulation mixture.The granulation mixture is placed in bell jar
In stove, under nitrogen atmosphere, by the granulation mixture first with 450 DEG C of Isothermal sinters 8 hours, then it is small with 750 DEG C of Isothermal sinters 6
When, and obtain lithium phosphate ferromanganese system powder (the specific surface area 14.2m of comparative example 2 after naturally cooling to room temperature (25 DEG C)2/ g, shakes
Real density is 1.15g/cm3)。
With sweep electron microscope (manufacturer's model：Hitachi su8000) the observation lithium phosphate ferromanganese system powder of comparative example 2
Body, Fig. 5 and Fig. 6 photos show that the lithium phosphate ferromanganese system particle in the lithium phosphate ferromanganese system powder of comparative example 2 is by multiple lithium phosphates
Manganese Fe nanomaterial (average grain diameter is by 250nm), which is combined together, to be formed.And (analytical instrument is via elementary analysis
PerkinElmer Optima 7000DV), the stoichiometric composition for learning lithium phosphate manganese Fe nanomaterial is
Li1.02Mn0.8Fe0.15Mg0.05PO4。
[properties evaluations]
Respectively the button type lithiums of CR 2032 electricity is made into using the lithium phosphate ferromanganese system powder of embodiment 1, comparative example 1 and 2
Pond, then heat analysis and every electrochemical properties are carried out with the button type lithium batteries of CR 2032 of embodiment 1, comparative example 1 and 2
Test.Wherein, details are as follows for the production method of the button type lithium batteries of CR 2032：
Negative electrode：By mixture, the polyvinylidene fluoride of lithium phosphate ferromanganese system powder, graphite and carbon black
(polyvinylidene fluoride) is according to weight than 93：3：4 mixing, add 6g 1-METHYLPYRROLIDONE (N-
Methyl-2-pyrrolidone) it is well mixed and forms a slurry.The slurry is coated on into an aluminium foil using scraper, and (thickness is
20 μm) surface after, then by the aluminium foil be placed in a heating platform drying after carry out vacuum drying again, to remove N- methylpyrroles
Alkanone, obtain a negative electrode.The negative electrode is first rolled cut into again a diameter of 12mm coin type it is standby.
Anode：The material of anode is lithium metal, thickness 0.3mm, a diameter of 1.5cm.
Electrolyte：1M lithium hexafluoro phosphate (LiPF6) be dissolved in ethylene carbonate (ethylene carbonate, EC),
Methyl ethyl carbonate (ethylmethyl carbonate, EMC) and dimethyl carbonate (dimethyl carbonate, DMC) (body
Product is than being 1：1：1) in the solvent formed.
According to the existing button type lithium battery production methods of CR 2032, and use above-mentioned negative electrode, anode and electrolyte
Manufacture embodiment 1, the button type lithium batteries of CR 2032 of comparative example 1 and 2.
1.0.1C current charge-discharge electrical testing (Capacity)
The button type lithium batteries of CR 2032 by embodiment 1, comparative example 1 and 2 in charging and discharging currents are 0.1C, voltage range
For 2.7 to 4.25V, the discharge capacity of the button type lithium batteries of CR 2032 is measured.Measurement is as shown in Figure 7.
2.0.1C, 1.0C, 5.0C, 10.0C discharge current test (C-rate)
The button type lithium batteries of CR 2032 by embodiment 1, comparative example 1 and 2 in charging current are 1.0C, operating voltage model
Enclose for 2.7 to 4.25V, measure the button type lithium batteries of CR 2032 respectively when discharge current is 0.1C, 1.0C, 5.0C and 10.0C
Discharge capacity first.Measurement is as shown in Figure 8.
3. charge and discharge cycles test (Cycle life) during high temperature
By embodiment 1, environment of the button type lithium batteries of CR 2032 at 55 DEG C of comparative example 1 and 2, electric current is determined with 2.0C
2.7 to 4.25V voltage ranges discharge and recharge 200 times.Measurement is as shown in Figure 9.
4. heat analysis tests (Safety)
By embodiment 1, comparative example 1 and 2 the button type lithium cell chargings of CR 2032 to after 4.25V, disassembling button type lithium electricity
Pond, negative electrode is removed, and the lithium phosphate ferromanganese system powder on negative electrode is scraped.The 3 milligrams of lithium phosphate scraped ferromanganese system powders are taken to put
Enter aluminium crucible, and add 3 μ l electrolyte, then aluminium crucible riveted is sealed, then show that difference scans analyzer (DSC, factory using heat
Business's model：PerkinElmer DSC7) heat analysis test is carried out, aluminium crucible is heated with 5 DEG C/min programming rate, scans temperature
Scope is 200 to 350 DEG C, and temperature during 5% weight loss occurs for record aluminium crucible, is heat decomposition temperature Td.Measurement is such as
Shown in Figure 10.
From Fig. 7 discharge capacity test result, the discharge capacity of the button type lithium batteries of CR 2032 of embodiment 1
Measure as 146.7mAh/g, the discharge capacity of the button type lithium batteries of CR 2032 of comparative example 1 is 144.2mAh/g, comparative example 2
The discharge capacity of the button type lithium batteries of CR 2032 is 132.8mAh/g.
From Fig. 8 test result, in 0.1C, 1.0C, 5.0C and 10.0C discharge current, the CR of embodiment 1
2032 button type lithium batteries are respectively provided with higher discharge capacity.And under 10C discharge current, the buttons of CR 2032 of embodiment 1
The capacitance of button-type lithium battery still possesses 75% capacitance compared with its discharge current in 0.1C, and the CR of comparative example 1 and 2
The capacitance of 2032 button type lithium batteries then distinguishes the capacitance of only residue about 68% and 47%.
The result tested from Fig. 9 55 DEG C of high temperature circulations, after discharge and recharge 200 times, the buttons of CR 2032 of embodiment 1
Button-type lithium battery also maintains 97% (142.2 ÷ 146.1 × 100%) of initial quantity of electricity, and the button type lithium battery of comparative example 1 only remains
82% (116.6 ÷ 142.5 × 100%) of lower initial quantity of electricity, the button type lithium battery of comparative example 2 are left the 98% of initial quantity of electricity
(121.6 ÷ 124.1 × 100%).
The result tested from Figure 10 heat analysis, after by button type lithium cell charging to 4.25V, by embodiment
The heat decomposition temperature for the lithium phosphate ferromanganese system powder that the button type lithium batteries of 1CR 2032 scrape is 288.2 DEG C, and thermal discharge is
84.5J/g.And lithium phosphate ferromanganese system powder the putting after thermal decomposition scraped by comparative example 1 and the button type lithium batteries of 2CR 2032
Heat is respectively 192.9J/g and 112.7J/g.
Therefore, complex chart 7 to Figure 10 test result are understood, compared to the lithium phosphate ferromanganese system powder of comparative example 1 to 2,
The lithium phosphate ferromanganese system powder of embodiment 1, which can enable, lithium battery while has higher energy density, outstanding high temperature circulation concurrently
Power, and preferable heat endurance.
In summary, lithium phosphate ferromanganese system powder preparation method of the present invention is made obtained by the step (A) to (E)
Lithium phosphate ferromanganese system particle in lithium phosphate ferromanganese system powder is general nucleation hull shape, and the of its shell portion of particle of lithium phosphate ferromanganese system
Second average grain diameter of diphosphonic acid lithium manganese Fe nanomaterial is more than the first of the first lithium phosphate manganese Fe nanomaterial in core portion
Average grain diameter, lithium phosphate ferromanganese system's powder enable to the energy density of lithium battery high, hot steady as the cathode material of lithium battery
Qualitative height, and the charge and discharge cycles good stability in high temperature, therefore the purpose of the present invention can be reached really.
As described above, only embodiments of the invention are every when the scope that the present invention can not be limited with this implement
The simple equivalent changes and modifications made according to claims of the present invention and description, all still belong to the model that the present invention covers
In enclosing.
Claims (12)
1. a kind of lithium phosphate ferromanganese system particle, suitable for the cathode material as lithium battery, the lithium phosphate ferromanganese system particle, its
It is characterised by that it is included：
One core portion, including multiple first lithium phosphate manganese Fe nanomaterials, the first lithium phosphate manganese Fe nanomaterial are knots
It is combined and there is one first average grain diameter；And
One shell portion, the core portion is coated, and including multiple second lithium phosphate manganese Fe nanomaterials, the second lithium phosphate ferromanganese
It is that nano-particle is bound together and has one second average grain diameter, and second average grain diameter is more than described first and is averaged
Particle diameter.
2. lithium phosphate ferromanganese system particle according to claim 1, wherein, the first lithium phosphate manganese Fe nanomaterial
The scope of first average grain diameter is 30 to 150nm.
3. lithium phosphate ferromanganese system particle according to claim 1, it is characterised in that the second lithium phosphate ferromanganese system nanometer
The scope of second average grain diameter of particle is 150 to 400nm.
4. lithium phosphate ferromanganese system particle according to claim 1, it is characterised in that first lithium phosphate in the core portion
The stoichiometric composition of manganese Fe nanomaterial and the chemistry meter of the second lithium phosphate manganese Fe nanomaterial in the shell portion
Amount composition is identical.
5. lithium phosphate ferromanganese system particle according to claim 4, it is characterised in that the first lithium phosphate ferromanganese system nanometer
The stoichiometric composition of particle and the second lithium phosphate manganese Fe nanomaterial is LixMn1-y-zFeyMzPO4, and 0.9≤x≤
The condition of 1.2,0.1≤y≤0.4,0≤z≤0.1, and 0.1≤y+z≤0.4, wherein, M be selected from magnesium, calcium, strontium, cobalt, titanium,
Zirconium, nickel, chromium, zinc, aluminium or an above-mentioned combination.
6. lithium phosphate ferromanganese system particle according to claim 1, it is characterised in that the first lithium phosphate ferromanganese system nanometer
Particle be by sinter bonded together, and the second lithium phosphate manganese Fe nanomaterial is one by sinter bonded
Rise.
A kind of 7. lithium phosphate ferromanganese system powder, suitable for the cathode material as lithium battery, it is characterised in that the lithium phosphate manganese
Iron system powder includes multiple lithium phosphate ferromanganese system particles as any one of claim 1 to 6.
8. lithium phosphate ferromanganese system powder according to claim 7, it is characterised in that the lithium phosphate ferromanganese system particle is put down
Equal particle size range is 0.6 to 20 μm.
9. lithium phosphate ferromanganese system powder according to claim 7, it is characterised in that the ratio of the lithium phosphate ferromanganese system powder
The scope of surface area is 5 to 30m2/g。
10. lithium phosphate ferromanganese system powder according to claim 7, it is characterised in that the lithium phosphate ferromanganese system powder
Tap density scope is more than 0.5g/cm3。
11. a kind of lithium phosphate ferromanganese system raw powder's production technology, it is characterised in that it is comprised the steps of：
(A) admixture containing a lithium source, a manganese source, a source of iron and a phosphorus source is provided；
(B) admixture is ground and is granulated to form a granulation mixture；
(C) granulation mixture is subjected to a preliminary sintering processes to form a pre-formed articles, wherein, at the preliminary sintering
The temperature range of reason is 300 to 450 DEG C；
(D) pre-formed articles are subjected to an intermediate sintering processing to form the pre-formed articles once intermediate sintering, wherein, it is described
The temperature range of intermediate sintering processing is more than 450 to 600 DEG C；And
(E) pre-formed articles through intermediate sintering are subjected to a last sintering processes to form lithium phosphate ferromanganese system powder, its
In, the temperature range of the last sintering processes is more than 600 to 800 DEG C.
12. lithium phosphate ferromanganese system raw powder's production technology according to claim 11, it is characterised in that the admixture is also
Containing one selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminium or the doping metals source of above-mentioned one combination.
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