CN105428637B - Lithium ion battery and preparation method of anode material thereof - Google Patents
Lithium ion battery and preparation method of anode material thereof Download PDFInfo
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- CN105428637B CN105428637B CN201410479797.8A CN201410479797A CN105428637B CN 105428637 B CN105428637 B CN 105428637B CN 201410479797 A CN201410479797 A CN 201410479797A CN 105428637 B CN105428637 B CN 105428637B
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Abstract
The invention discloses a lithium ion battery, a positive electrode material and a preparation method thereof. The positive electrode material is a lithium-rich manganese-based positive electrode material coated on the surface of a fast ion conductor material and is prepared by adopting a liquid phase method; the lithium ion battery is a battery using the above-described positive electrode material as a positive electrode active material. Compared with the prior art, the lithium ion battery anode material adopts the fast ion conductor as the surface coating, so that the rate capability and the high-voltage cycling stability are greatly improved, and the battery using the fast ion conductor as the anode active substance has the advantages of good rate capability, high specific capacity, strong cycling stability, high primary efficiency and the like.
Description
Technical field
The invention belongs to field of lithium ion battery, it is more particularly related to a kind of positive electrode and its preparation side
Method.
Background technique
The key factor of limiting lithium ion cell energy density promotion at present and price, mainly in positive electrode side
Face.Existing positive electrode is mainly with stratiform LiCoO in the market2Based on, spinel lithium manganate, layered lithium manganate, stratiform nickel cobalt
LiMn2O4, olivine lithium iron phosphate etc. also respectively occupy certain market share.In these materials, LiCoO2Be be commercialized most at
One of ripe material occupies the very big market share especially in consumption electronic product；But it is dilute that shortcoming is that Co belongs to
Resource is lacked, it is expensive, it also can cause environmental pollution, and structure becomes unstable after voltage is higher than 4.3V, causes
Secure context is also a very big challenge.Manganese systems LiMnO2Have many advantages, such as that cheap, theoretical capacity is high, but at the material
In a kind of thermodynamic instability state, not only prepare it is extremely difficult, but also in charge and discharge process it also occur that layer structure to
The transformation of spinel structure causes capacity attenuation ratio in cyclic process very fast, and chemical property is unstable；Manganese systems LiMn2O4Energy
It is enough to make up LiMnO to a certain extent2Deficiency, but be but easy the dissolution for occurring manganese ion in cyclic process, especially
At high temperature, the dissolution of manganese can be exacerbated, and LiMn2O4In manganese ion Jahn-Teller effect easily occurs, cause to recycle
Attenuation ratio is very fast and high-temperature behavior is undesirable.And LiFePO4Although raw material is extensive, cheap, also there is excellent circulation
Many advantages, such as performance, security performance and thermal stability, but working voltage platform is relatively low, thus battery pair can not be met
The requirement of high-energy density.In contrast, there is the stratiform ternary material Li-Ni-Co-Mn of three metal ion species synergistic effects more
The deficiency of above-mentioned stratified material has been mended, has had specific capacity height, good cycle, security performance stabilization, synthesis and preparation process simple
The advantages that, it is regrettable that, the specific capacity of such material is still within 200mAh/g, so as to battery energy density
Promotion has certain limitation.
The study found that excessive addition lithium can obtain a kind of new rich lithium manganese base solid solution in above-mentioned stratiform ternary material
Positive electrode, the material can be considered Li2MnO3With LiMO2(M Co, Fe, Ni, NixCoy、NixCoyMnz) solid solution, specific volume
Amount be higher than 250mAh/g (being the practical gram volume of positive electrode current material more than 2 times), and have stable structure, cheap price,
Wider charging/discharging voltage range, good security performance and excellent cyclical stability, this receives the material extensively
It pays close attention to generally, and is considered as the preferred positive electrode of next-generation lithium ion battery by numerous scholars and industrial circle.But though material
Right actual specific capacity with higher, charge-discharge magnification is but very low, and after charge-discharge magnification increase, specific capacity declines quickly,
Show very poor high rate performance；In addition, the material is only charged on 4.5V, by Li2MnO3Just have after activation very high
Specific capacity can also be such that material structure is destroyed under high voltage.As it can be seen that not reach high-energy close for the actual performance of the material
The requirement of degree, therefore there is an urgent need to be modified to it, enable it to the structure under high rate performance, first charge discharge efficiency, high voltage
Stability etc. is greatly improved, to realize industrial applications as early as possible.
Currently, industry has done many work in terms of the cyclical stability for improving above-mentioned stratiform ternary material, also obtain
Certain effect, such as: utilize Al2O3To Li1.2Ni0.13Co0.13Mn0.54After being coated, cycle performance and high rate performance
Very big improvement is obtained, after recycling 50 times, capacity retention ratio is also increased to 94% from 90%；Utilize TiO2And AlF3Cladding
Li1.2Ni0.13Co0.13Mn0.54, while first charge-discharge efficiency, which obtains, to be improved, the cycle performance at 55 DEG C is also obtained
Significantly improve.As it can be seen that above-mentioned method for coating is really to the first charge discharge efficiency and stable circulation for improving Li-Ni-Co-Mn ternary material
Property aspect have very great help, but since these covering materials itself have poor ionic conductivity, so leading to cladding side
Method does not have too big help in terms of improving multiplying power.In addition, it is thus proposed that using fast-ionic conductor, mutually modification is mixed with rare earth element
Miscellaneous lithium-rich manganese-based anode material for lithium-ion batteries, this method equally achieve in terms of cycle performance and high rate performance centainly
Effect, and extend the charge and discharge temperature range of battery；But due to Li in lithium-rich manganese base material2MnO3Structure itself do not have
It is activated, and uses Solid phase synthesis, hardly result in nanoscale between different materials particle and uniformly mix, therefore to high rate performance
Improvement receive certain limitation.
In view of this, it is necessory to provide a kind of surface modifying method that can prepare high capacity lithium-rich manganese-based anode material,
To improve the deficiency of existing lithium-rich manganese-based anode material.
Summary of the invention
It is an object of the invention to: a kind of surface coated lithium-rich manganese-based anode material and preparation method thereof is provided, to change
It is apt to the deficiency of existing lithium-rich manganese-based anode material.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of positive electrodes comprising bulk material Li
[Li(1-2x)/3MxMn(2-x)/3]O2With the fast ion conducting material for being coated on bulk material surface；In the bulk material, M is selected from
At least one of Ni, Co, Cr, x are 0~0.33；Lithium ion in fast ion conducting material is located at four sides position, and can join
Deintercalation with lithium ion and the lithium ion for making up bulk material consumption；Fast ion conducting material accounts for bulk material and fast-ionic conductor
The percentage of material gross mass is 0.5%~12%.
Compared with prior art, positive electrode of the present invention uses tetrahedral fast-ionic conductor as surface cover,
Therefore cyclical stability is effectively improved under high rate performance and high voltage, to make with it as a positive electrode active material
Battery have many advantages, such as that good rate capability, specific capacity are high, cyclical stability is strong, first charge discharge efficiency is high.
As a kind of improvement of positive electrode of the present invention, the fast-ionic conductor is Li3V2(PO4)3、Li2ZrS3、Li2O-
mB2O3One or more of.
In order to achieve the above-mentioned object of the invention, the present invention also provides a kind of method for preparing anode material comprising following step
It is rapid:
1) raw material for preparing fast-ionic conductor are dissolved in solvent, 5~50ml acid are added, and in 60~120 DEG C of water-baths
Under the conditions of stirred with the revolving speed of 70~240r/min；
2) amount that fast-ionic conductor is 0.5%~12% with bulk material total mass fraction is accounted for according to fast-ionic conductor to weigh
Li[Li(1-2x)/3MxMn(2-x)/3]O2Powder is suspended in solution made of step 1), is continued under 60~120 DEG C of water bath conditions,
First ultrasound 1h~6h, then stirring makes Li [Li(1-2x)/3MxMn(2-x)/3]O2Powder is evenly dispersed in the solution, and finally by solution
In all solvent evaporate, obtain uniformly mixed composite material；Li[Li(1-2x)/3MxMn(2-x)/3]O2M choosing in powder
It is 0~0.33 from least one of Ni, Co, Cr, x；
3) composite material for obtaining step 2) calcines 3~20h at 300~600 DEG C, and surface can be obtained and be coated with fastly
The positive electrode of ion conductor.
Compared with prior art, the present invention prepares the surface coated lithium-rich manganese-based anode material of fast-ionic conductor using liquid phase method
Material, has at least the following advantages:
1) mixing of ion nanoscale may be implemented in wet chemical methods, so that modified ion is more uniformly coated on bulk material
Surface and improve its performance；
2) using having lithium to coat bulk material lithium-rich manganese-based anode material in the fast ion conducting material of four sides position,
It is prepared by liquid phase method, fast-ionic conductor can be uniformly distributed in the surface of bulk material, inhibit transition metal in bulk material
Dissolution and side reaction generation, the positive electrode can be effectively prevented and react under high blanking voltage with electrolyte destruction
Material structure, and then its cycle performance in operating voltage range is improved, the high rate performance of the material is greatly improved,
And also there is significantly effect in terms of voltage platform after inhibiting circulation；
3) in addition, in step 1 sour introducing can make bulk material Li [Li(1-2x)/3MxMn(2-x)/3]O2Middle Li2MnO3
Structural unit is activated first, while increasing ionic conduction, is played the capacity of bulk material farthest, is reached
To the requirement of high-energy density；
4) have many advantages, such as that process route is simple, technological parameter is easy to control, process is short, no pollution to the environment, be suitble to big
Large-scale production, therefore there is wide large-scale production prospect.
A kind of improvement of preparation method as positive electrode of the present invention, the step 1) and 2) in fast-ionic conductor be
Refer to Li3V2(PO4)3、Li2ZrS3、Li2O-mB2O3One or more of.
A kind of improvement of preparation method as positive electrode of the present invention prepares the original of fast-ionic conductor in the step 1)
Material is selected by the fast-ionic conductor of required preparation, and each element in fast-ionic conductor is respectively from following raw material:
Li element comes from Li compound, specifically includes lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, one in lithium sulfate
Kind is several；
B element is from one or more of boric acid, carbonic acid boron and diboron trioxide；
V element comes one or more of self-bias alum acid ammonium, vanadic anhydride, vanadium trioxide；
Al element comes from one or more of aluminium acetate, aluminum nitrate, aluminium chloride, aluminum sulfate；
Si element comes from one or more of silica, silicic acid, sodium metasilicate；
Zr element comes from one or more of zirconium dioxide, chlorine monoxid zirconium, zirconium sulfate, zirconium nitrate；
S element comes from one or more of sodium sulphate, vulcanized sodium；
P element comes from one or more of ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.
A kind of improvement of preparation method as positive electrode of the present invention, the Li [Li in the step 2)(1-2x)/ 3MxMn(2-x)/3]O2Powder is prepared using existing method, can also be prepared, be wrapped using the new method of subsequent development
Include but be not limited to solid phase method, hydroxide or carbonate or oxalate precipitation process, combustion method or sol-gal process etc..
A kind of improvement of preparation method as positive electrode of the present invention, the acid in the step 1) can be selected from sulfuric acid, salt
Acid, nitric acid.
A kind of improvement of preparation method as positive electrode of the present invention, the solvent in the step 1) can be selected from deionization
Water, dehydrated alcohol.
In order to achieve the above-mentioned object of the invention, invention further provides a kind of lithium ion battery, including positive plate, negative electrode tab,
The isolation film and electrolyte being interval between positive/negative plate, positive plate include plus plate current-collecting body and are distributed in plus plate current-collecting body
On positive active material, negative electrode tab includes negative current collector and the negative electrode active material that is distributed on negative current collector, wherein
Positive active material is surface coated lithium-rich manganese-based anode material described in any of the above-described paragraph.
Compared with prior art, lithium ion battery of the present invention using above-mentioned fast-ionic conductor it is surface coated it is lithium-rich manganese-based just
Pole material as a positive electrode active material, therefore has very high discharge capacity, excellent high rate performance, stable cycle performance.
Detailed description of the invention
With reference to the accompanying drawings and detailed description, to anode material for lithium-ion batteries of the present invention, preparation method, use this
Lithium ion battery made from positive electrode and its advantages are described in detail.
Fig. 1 is Li made from the embodiment of the present invention 12O-mB2O3Coat the SEM figure of lithium-rich manganese-based anode material.
Fig. 2 is Li made from the embodiment of the present invention 12O-mB2O3Coat the XRD diagram of lithium-rich manganese-based anode material.
Fig. 3 be use positive electrode made from the embodiment of the present invention 1 be the button cell of positive active material 30mA electricity
First charge-discharge curve graph under current density.
Fig. 4 is that use positive electrode made from the embodiment of the present invention 1 be the button cell of positive active material in different electricity
Cyclic curve figure under current density.
Fig. 5 be use positive electrode made from the embodiment of the present invention 2 be the button cell of positive active material 30mA electricity
Cyclic curve figure under current density.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention will be described in further detail.It should be understood that embodiment described in this specification is just for the sake of explanation
The present invention, be not intended to limit the present invention, formula, ratio of embodiment etc. can adaptation to local conditions make a choice and reality had no to result
Matter influences.
Embodiment 1
Prepare positive electrode:
A) lithium hydroxide and boric acid are weighed for the ratio of 1:0.5 in molar ratio, after it is dissolved into deionized water respectively,
10ml nitric acid is added, and at a temperature of 80 DEG C, is stirred to dissolve with the revolving speed of 70r/min；
B) according to Li2O-mB2O3It accounts for the mass fraction of bulk material and fast ion conducting material and weighs Li for 0.5%
[Li0.22Ni0.17Mn0.61]O2Dusty material is suspended to it in a) solution, continues first ultrasound 1h under conditions of 80 DEG C of water-baths
Afterwards, it is followed by stirring for making Li [Li0.22Ni0.17Mn0.61]O2Powder is dispersed in a solution, will be owned in solution after being uniformly dispersed
Solvent evaporates, and obtains uniformly mixed composite material；
C) mixing material for obtaining step b is heat-treated 3h at 350 DEG C to get fast-ionic conductor Li is arrived2O-mB2O3Packet
The lithium-rich manganese-based anode material covered.
Fig. 1 and Fig. 2 is respectively Li2O-mB2O3The SEM of the lithium-rich manganese-based anode material of cladding schemes and XRD diagram, from Fig. 1 and figure
As can be seen that using liquid phase method in 2, the surface for being distributed in bulk material of coating more evenly can be made, and there is no impurity phase
In the presence of.
It prepares battery and is tested:
With Li2O-mB2O3Li [the Li of fast-ionic conductor cladding0.22Ni0.17Mn0.61]O2For positive active material, by its with
Conductive agent, binder press the mass ratio of 85:10:5, uniformly mix, are then coated in aluminium foil in N-methyl pyrrolidones (NMP)
On collector, it is placed under vacuum environment and obtains positive plate after drying at 120 DEG C；Using metal lithium sheet as cathode, according to conventional side
Method is assembled into button cell.Constant current charge-discharge test is carried out at room temperature to the button cell assembled, wherein test voltage model
It encloses for 2.0~4.8V.The results show that using battery made from positive electrode of the present embodiment by cladding processing, electric discharge is held
Amount reaches 297mAh/g, and first charge discharge efficiency is up to 89%, 98.8% after recycling 50 times.
Embodiment 2
Prepare positive electrode:
A) Li is weighed according to the ratio that molar ratio is 1.5:1:1.52CO3、V2O5And NH4H2PO4, it is dissolved into anhydrous second
In alcohol, 50ml hydrochloric acid is added, and at a temperature of 80 DEG C, is stirred to dissolve with the revolving speed of 150r/min；
B) according to Li3V2(PO4)3The mass fraction 5% for accounting for bulk material and fast ion conducting material weighs Li
[Li0.14Ni0.15Co0.14Mn0.57]O2Dusty material is suspended to it in a solution, continues first ultrasonic under conditions of 80 DEG C of water-baths
After 1h, it is followed by stirring for making its Li [Li0.14Ni0.15Co0.14Mn0.57]O2Powder is dispersed in a) solution, will after being uniformly dispersed
All solvents evaporate in solution, obtain uniformly mixed composite material；
C) mixing material for obtaining step b is heat-treated 10h at 500 DEG C to get fast-ionic conductor Li is arrived3V2(PO4)3
The lithium-rich manganese-based anode material of cladding.
It prepares battery and is tested:
According to the method for embodiment 1, using Li3V2(PO4)3The Li of fast-ionic conductor cladding
[Li0.14Ni0.15Co0.14Mn0.57]O2Material is positive active material, is assembled into button cell, in 2.0~4.8V voltage range
Charge-discharge test is carried out with 0.1C electric current.The results show that the discharge capacity of battery is 298mAh/g, first charge discharge efficiency 91%；Together
When, by adjusting charging/discharging voltage range, very high capacity is also obtained, the charge and discharge such as between 2.0~4.6V, battery capacity
275mAh/g is reached, it is 98.3% after circulation 50 times that first charge discharge efficiency, which is up to 88%,.
Embodiment 3
Prepare positive electrode:
A) Li is weighed according to the ratio that molar ratio is 1:1:12CO3、Al(NO3)3And SiO2, it is dissolved into dehydrated alcohol
In, 15ml sulfuric acid is added, and at a temperature of 80 DEG C, stir to dissolve with the revolving speed of 240r/min；
B) according to Li2O-AlO-SiO2The mass fraction 12% for accounting for bulk material and fast ion conducting material weighs Li
[Li0.3Cr0.05Mn0.65]O2Dusty material is suspended to it in a) solution, continues first ultrasound 1h under conditions of 80 DEG C of water-baths
Afterwards, it is followed by stirring for making its Li [Li0.3Cr0.05Mn0.65]O2Powder is dispersed in a solution, by institute in solution after being uniformly dispersed
There is solvent to evaporate, obtains uniformly mixed composite material；
C) mixing material for obtaining step b is heat-treated 20h at 600 DEG C to get fast-ionic conductor Li is arrived2O-AlO-
SiO2The lithium-rich manganese-based anode material of cladding.
It prepares battery and is tested:
According to the method for embodiment 1, using Li2O-AlO-SiO2Li [the Li of fast-ionic conductor cladding0.3Cr0.05Mn0.65]O2
For positive active material, it is assembled into button cell, carries out charge-discharge test with 0.1C electric current in 2.0~4.8V voltage range,
The discharge capacity for obtaining battery is 290mAh/g, and first charge discharge efficiency 89%, circulation 50 times are 97.2% later；Meanwhile using not
Same current density carries out cycle charge-discharge, and discovery has excellent multiplying power by the lithium-rich manganese-based anode material that fast-ionic conductor coats
Performance and stable cycle performance.
Embodiment 4
Prepare positive electrode:
A) Li is weighed according to the ratio that molar ratio is 1.5:1:1.52CO3、V2O5And NH4H2PO4, it is dissolved into anhydrous second
In alcohol, 5ml nitric acid is added, and at a temperature of 80 DEG C, is stirred to dissolve with the revolving speed of 80r/min；
B) according to Li3V2(PO4)3The mass fraction 7% for accounting for bulk material and fast ion conducting material weighs Li
[Li0.16Cr0.15Ni0.18Mn0.51]O2Dusty material is suspended to it in a) solution, and continuation first surpasses under conditions of 80 DEG C of water-baths
After sound 1h, it is followed by stirring for making its Li [Li0.16Cr0.15Ni0.18Mn0.51]O2Powder is dispersed in a solution, will after being uniformly dispersed
All solvents evaporate in solution, obtain uniformly mixed composite material；
C) mixing material for obtaining step b is heat-treated 12h at 550 DEG C to get fast-ionic conductor Li is arrived3V2(PO4)3
The lithium-rich manganese-based anode material of cladding.
It prepares battery and is tested:
According to the method for embodiment 1, using Li3V2(PO4)3The Li of fast-ionic conductor cladding
[Li0.16Cr0.15Ni0.18Mn0.51]O2Material is positive active material, is assembled into button cell, in 2.0~4.8V voltage range
Charge-discharge test is carried out with 0.1C electric current, the discharge capacity for obtaining battery is 295mAh/g, and first charge discharge efficiency 90% recycles 50 times
It is later 98.1%.
Comparative example 1
With used without by coating processed Li [Li in embodiment 10.22Ni0.17Mn0.61]O2As positive electrode active material
It is pressed the mass ratio of 85:10:5 with conductive agent, binder, uniformly mixed in N-methyl pyrrolidones (NMP), then by matter
Positive plate is obtained coated in aluminum foil current collector, being placed under vacuum environment at 120 DEG C after drying；Using metal lithium sheet as cathode,
It is conventionally assembled into button cell, constant current charge-discharge test is carried out at room temperature to the button cell assembled, in electricity
Pressing range is to carry out charge and discharge in 2.0~4.8V with 0.1C electric current, and the discharge capacity for obtaining battery is 241mAh/g, first charge discharge efficiency
It is 78%, is 85% after circulation 50 times.
Comparative example 2
According to Li3V2(PO4)3Mass fraction 7% weigh Li [Li0.16Cr0.15Ni0.18Mn0.51]O2Dusty material, and
Using ethyl alcohol as medium, the mechanical activation 2h in fixed star ball mill, by gained presoma after 80 DEG C are dry, resulting mixture material
Material with 550 DEG C at high-temperature heat treatment 12h to get arriving fast-ionic conductor Li3V2(PO4)3The lithium-rich manganese-based anode material of cladding.
The assembling of button cell
Respectively using positive electrode made from Examples 1 to 4 and comparative example 1~2 as positive active material, by itself and conduction
The mass ratio of 85:10:5 is pressed in agent, binder, is uniformly mixed, is then coated in aluminium foil afflux in N-methyl pyrrolidones (NMP)
It on body, is placed under vacuum environment and obtains positive plate after drying at 120 DEG C, be then washed into the sequin that diameter is 2mm；And
And using metal lithium sheet as cathode, with LiPF6/ EC+DMC is electrolyte, using PP or PE as isolation film, in the hand for being full of inert gas
2032 type button cells are assembled into casing.
Battery performance test
At room temperature, the button cell assembled to Examples 1 to 4 and comparative example 1~2 is first arrived with 0.1C constant-current charge
4.8V after standing 3min, then with 0.1C constant-current discharge to 3.0V, records the initial charge that current charging capacity is the material and holds
Amount, discharge capacity are the discharge capacity for the first time of the material, and the ratio of discharge capacity and initial charge capacity is the material for the first time
First charge discharge efficiency.Cycle performance test is tested using identical multiplying power is charged and discharged, 1 institute of test result such as Fig. 3-5 and table
Show.
The battery performance test result of table 1, Examples 1 to 4 and comparative example 1~2
From Fig. 3-5 and table 1 it can be seen that
1) it can be seen that the fast-ionic conductor for being located at four sides position by Li from the test result of embodiment 1 and comparative example 1
Processed lithium-rich manganese-based anode material for lithium-ion batteries is coated not only in discharge capacity for the first time, high rate performance and cyclicity side
Face has clear improvement, and has also obtained greatly improving in terms of first charge discharge efficiency, this is primarily due to by fast-ionic conductor
The dissolution of lithium-rich manganese-based anode material after cladding manganese under high voltages is suppressed and improves cycle performance；In addition, fast ion
Conductor has faster ionic conductivity, and Li is located at four sides position and can identify oneself with the deintercalation of lithium ion, therefore mentions
High first charge discharge efficiency and improve high rate performance；
2) it can be seen that from the test result of embodiment 1 and comparative example 2 by Li3V2(PO4)3Coat processed rich lithium
Manganese-based anode material has improvement in terms of cycle performance, this is consistent with the result of fast-ionic conductor cladding processing, can inhibit high
The structure of the dissolution of manganese and stable bulk material under voltage；But discharge capacity and first charge discharge efficiency difference are more apparent for the first time, it is main
Liquid phase method used due to embodiment 1, be conducive to uniformly mix between different materials particle to nanoscale, furthermore sour in liquid phase added
Enter, Li in lithium-rich manganese base material can be made2MnO3Structure be activated, so that capacity in its bulk material is not fully exerted, for the first time
Discharge capacity and first charge discharge efficiency are higher；
3) it can be seen that embodiment 2 to lithium-rich manganese-based lithium ion cell positive from the comparison of embodiment 2 and embodiment 1,3
The treatment effect of material is more preferable, this may be since V ion has and more appraises at the current rate in the fast-ionic conductor in embodiment 2, when
When participating in the deintercalation reaction of lithium positioned at the Li of four sides position, V ion can carry out the adjustment of valence state, but overall structure will not be by
To micro- destruction, to preferably improve the performance of bulk material.
In conclusion coating one layer of fast-ionic conductor that there is Li to be located at four sides position on lithium-rich manganese base material surface, especially
It is Li3V2(PO4)3Fast-ionic conductor can make lithium-rich manganese base material not only in discharge capacity for the first time, forthright again and follow
It gets a promotion in terms of ring, and more importantly can significantly improve the first charge discharge efficiency of the material, while inhibiting circulation
The decline of voltage platform in the process.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (6)
1. a kind of preparation method of positive electrode, which comprises the following steps:
1) raw material for preparing fast-ionic conductor are dissolved in solvent, are added 5~50ml sulfuric acid, hydrochloric acid or nitric acid, and in 60~
It is stirred under 120 DEG C of water bath conditions with the revolving speed of 70~240r/min；
2) fast-ionic conductor and bulk material total mass fraction are accounted for according to fast-ionic conductor and weighs ontology for 0.5%~12% amount
Material Li [Li(1-2x)/3MxMn(2-x)/3]O2Powder is suspended in solution made of step 1), is continued in 60~120 DEG C of water bath conditions
Under, first ultrasound 1h~6h, then stirring makes Li [Li(1-2x)/3MxMn(2-x)/3]O2Powder is evenly dispersed in the solution, and finally will
All solvents evaporate in solution, obtain uniformly mixed composite material；Li[Li(1-2x)/3MxMn(2-x)/3]O2In powder
M is selected from least one of Ni, Co, Cr, and x is 0~0.33；
3) composite material for obtaining step 2) calcines 3~20h at 300~600 DEG C, can be obtained positive electrode, it is described just
Pole material includes bulk material Li [Li(1-2x)/3MxMn(2-x)/3]O2With the fast ion conducting material for being coated on bulk material surface；
Lithium ion in the fast ion conducting material is located at four sides position, and can participate in the deintercalation of lithium ion and make up bulk material
The lithium ion of consumption；Fast ion conducting material account for the percentage of bulk material and fast ion conducting material gross mass be 0.5%~
12%.
2. the preparation method of positive electrode according to claim 1, it is characterised in that: the step 1) and 2) in it is fast from
Sub- conductor refers to Li3V2(PO4)3、Li2ZrS3、Li2O-mB2O3One or more of.
3. the preparation method of positive electrode according to claim 2, it is characterised in that: prepare fast ion in the step 1)
The raw material of conductor are selected by the fast-ionic conductor of required preparation, and each element in fast-ionic conductor is respectively from following
Raw material: Li element comes from one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate；B element comes from
One or more of boric acid, carbonic acid boron and diboron trioxide；V element comes self-bias alum acid ammonium, vanadic anhydride, three oxidations two
One or more of vanadium；Al element comes from one or more of aluminium acetate, aluminum nitrate, aluminium chloride, aluminum sulfate；Si member is usually
From one or more of silica, silicic acid, sodium metasilicate；Zr element comes from zirconium dioxide, chlorine monoxid zirconium, zirconium sulfate, nitric acid
One or more of zirconium；S element comes from one or more of sodium sulphate, vulcanized sodium；P element comes from ammonium phosphate, phosphoric acid hydrogen
One or more of ammonium, ammonium dihydrogen phosphate.
4. the preparation method of positive electrode according to claim 1, it is characterised in that: the Li in the step 2)
[Li(1-2x)/3MxMn(2-x)/3]O2Powder uses solid phase method, hydroxide or carbonate or oxalate precipitation process, combustion method or colloidal sol
Gel method preparation.
5. the preparation method of positive electrode according to claim 1, it is characterised in that: the solvent in the step 1) is selected from
Deionized water, dehydrated alcohol.
6. a kind of lithium ion battery, including positive plate, negative electrode tab, the isolation film and electrolyte being interval between positive/negative plate,
Positive plate includes plus plate current-collecting body and the positive active material that is distributed on plus plate current-collecting body, negative electrode tab include negative current collector and
The negative electrode active material being distributed on negative current collector, it is characterised in that: the positive active material is in claim 1 to 5
The positive electrode that any one method is prepared.
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| CN106784731A (en) * | 2017-01-23 | 2017-05-31 | 宁德时代新能源科技股份有限公司 | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
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| WO2024036472A1 (en) * | 2022-08-16 | 2024-02-22 | 宁德时代新能源科技股份有限公司 | Positive electrode active material and preparation method therefor, positive electrode plate, secondary battery, battery module, battery pack and electric device |
| WO2024050654A1 (en) * | 2022-09-05 | 2024-03-14 | 宁德时代新能源科技股份有限公司 | Positive electrode active material precursor, positive electrode active material, preparation method and secondary battery |
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