CN107968195A - A kind of lithium-rich anode material of LiFePO4 cladding and preparation method thereof - Google Patents
A kind of lithium-rich anode material of LiFePO4 cladding and preparation method thereof Download PDFInfo
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Abstract
Lithium-rich anode material the invention discloses a kind of LiFePO4 cladding and preparation method thereof, belongs to technical field of lithium ion, which includes rich lithium material and the LiFePO4 for being coated on rich lithium material surface, its chemical formula is LiFePO4‑Li1.2Mn0.54Ni0.13Co0.13O2, structure is stratiform α NaFeO2Structure, the space group of stratiform is RThe mass percent of m, wherein LiFePO4 are 3 7%.The present invention passes through the LiFePO in lithium-rich anode surface cladding crystalline state4, the surface texture stability of material is improved, while extra discharge capacity can be provided（LiFePO4It is electro-chemical activity）The coulombic efficiency first of sample after cladding can reach 91.9%, and specific discharge capacity is up to 295mAh/g under 0.1C electric currents.The high rate performance of sample is greatly improved after cladding, and 5C multiplying powers discharge capacity can reach 201.8mAh/g, still have 183.8mAh/g after 50 circulations, significantly larger than uncoated sample.Preparation method of the present invention is simple, enhances surface texture, discharge capacity is high, and high rate performance and cycle performance are more preferably.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically a kind of LiFePO4 cladding lithium-rich anode material and its
Preparation method.
Background technology
It is mobile whole in recent years since the high speed development of the Internet, applications and people give more sustained attention global environmental problems
End (particularly smart mobile phone) and electric automobile field increase the demand of high energy density cells, big specific capacity and high workload electricity
The positive electrode of pressure receives increasing concern.Commercial positive electrode LiCoO at present2、LiMn2O4、LiFePO4And ternary
LiMnxCoyNi1-x-yO2Specific discharge capacity be below 200mAh/g.In contrast, rich lithium material xLi2MnO3·(1-x)LiMO2
The specific discharge capacity of 250mAh/g, while its high operating voltage, low production cost and advantages of environment protection are had more than,
In the case where continuing to develop in recent years, it is expected to as the anode material for lithium-ion batteries of a new generation.
Although lithium-rich anode material has the advantage of high reversible capacity and low cost, there is also the effect of coulomb first
The shortcomings of rate is low and cycle life is insufficient, seriously constrains the application of lithium-rich anode material in practice.Lithium-rich anode material
High power capacity derives from Li under high voltages during initial charge2MnO3Activation process, that is, Li in lattice2O's is irreversible
Abjection is at the same time with the generation of Lacking oxygen.Because this decomposition of irreversible activation process and electrolyte under high voltages,
It result in the low coulombic efficiency first of lithium-rich anode material.Lithium-rich anode material is from layer structure to spinelle in charge and discharge process
The transformation of structure is the main reason for causing lithium-rich anode material poor circulation.
In order to further improve its coulombic efficiency and cycle performance first, we are prepared for LiFePO with simple precipitation method4
The Li of cladding1.2Mn0.54Ni0.13Co0.13O2(LMNCO) lithium-rich anode material, back to back roasting process are used for strengthening interface
Structural stability.Compared to uncoated material, the lithium-rich anode material after cladding has specific discharge capacity, the high head of bigger
Cycle performance under secondary coulombic efficiency and good cycle performance, particularly high magnification.
The content of the invention
It is an object of the invention to overcome defect existing in the prior art, there is provided a kind of lithium-rich anode of LiFePO4 cladding
Material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium-rich anode material of LiFePO4 cladding, including rich lithium material and the phosphoric acid for being coated on rich lithium material surface
Iron lithium, its chemical formula are LiFePO4-Li1.2Mn0.54Ni0.13Co0.13O2, structure is stratiform α-NaFeO2Structure, the space of stratiform
Group beWherein the mass percent of LiFePO4 is 3-7%.
It is another object of the present invention to provide a kind of preparation method of the lithium-rich anode material of LiFePO4 cladding, bag
Include following steps：
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2：According to Li:Mn:Ni:The molar ratio of Co is 1.32:0.54:0.13:
0.13 weighs LiCOOCH3·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH3)2·4H2O, be dissolved in from
In sub- water, mixing salt solution is made into；According to citric acid：Metal ion=3:1, aqueous citric acid solution is added to mixing salt solution
In, 80 DEG C are heated to, magnetic stirring 4h, forms pink clear gel；Gel is moved into drying in air dry oven, box
Pre-burning 5h under 480 DEG C of air atmospheres in stove, takes out grinding, then moves into 900 DEG C of calcining 12h in Muffle furnace, is made
Li1.2Mn0.54Ni0.13Co0.13O2Powder；
(2) lithium-rich anode material of LiFePO4 cladding is prepared：According to molar ratio Li:Fe is 1:1 weighs respectively
LiCOOCH3·2H2O and FeSO4·7H2O, is dissolved in deionized water, according to molar ratio Li:P=1:1, by NH4H2PO4Aqueous solution
It is slowly dropped into wherein and is stirred continuously, is subsequently added into the Li of step (1) preparation1.2Mn0.54Ni0.13Co0.13O2Powder, heating sealing
Magnetic stirs, and is washed after standing 12h, is slightly ground after dry, moves into tube furnace the 300-500 DEG C of roasting 3- under protective atmosphere
5h, is made the lithium-rich anode material of LiFePO4 cladding.
Further scheme, step (1) drying temperature are 80 DEG C, drying time 12h.
Further scheme, the heating rates of 900 DEG C of calcinings are 4 DEG C/min in the step (1).
Further scheme, the middle heating sealing magnetic stirring of the step (2) are：60-100 DEG C is heated to, magnetic mixing speed is
80-180r/min, preferably mixing speed 160r/min, magnetic mixing time are 3-5h, preferably mixing time 4h.
Further scheme, the middle washing of the step (2) are to use deionized water and absolute ethyl alcohol centrifugal elutriation three times successively.
Further scheme, protective atmosphere is high-purity argon gas in the step (2).
Beneficial effects of the present invention：
1st, the present invention passes through the LiFePO in lithium-rich anode surface cladding crystalline state4, improve material surface texture stablize
Property, while extra discharge capacity (LiFePO can be provided4It is electro-chemical activity) effect of coulomb first of sample after cladding
Rate can reach 91.9%, and specific discharge capacity is up to 295mAh/g under 0.1C (1C=300mA/g) electric current.After particularly coating
The high rate performance of sample is greatly improved, and 5C multiplying powers discharge capacity can reach 201.8mAh/g, after 50 circulations still
So there is 183.8mAh/g, significantly larger than uncoated sample.
2nd, preparation method of the present invention is simple, enhances surface texture and (reduces and contacted with the direct of electrolyte, suppress the molten of Mn
Solution), discharge capacity is high, and high rate performance and cycle performance are more preferably.
Brief description of the drawings
Fig. 1 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) XRD spectrum.
Fig. 2 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) SEM figures；Wherein：(a) (b) LMNCO, (c) (d) LFP-400, (e) (f) LFP-500.
Fig. 3 is (a) LMNCO, (b) LFP-400, the HRTEM images of (c) LFP-500 samples, and the EDS of (d) LFP-400 schemes
Picture.
Fig. 4 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) first charge-discharge curve map.
Fig. 5 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) cyclic curve figure under (a) 1C and (b) 5C electric currents.
Fig. 6 is LFP-400, LFP-500 prepared by embodiment 2 and pure rich lithium material prepared by the embodiment of the present invention 1
(LMNCO) high rate performance figure.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Mn:Ni:Co is 1.32:0.54:0.13:0.13 ratio measures LiCOOCH3·2H2O, Mn
(COOCH3)2, Ni (COOCH3)2·4H2O, Co (COOCH3)2·4H2O, is dissolved in 100mL deionized waters, it is molten to obtain salt-mixture
Liquid；Then a certain amount of citric acid (citric acid：Metal ion=3:1 molar ratio) it is dissolved in 50mL deionized waters and stirs evenly；
Aqueous citric acid solution is slowly dropped in mixing salt solution, 80 DEG C, when magnetic stirring 4 is small is heated to, it is transparent solidifying to form pink
Glue, when gel is moved into 80 DEG C of dryings 12 are small in air dry oven, when pre-burning 5 is small under 480 DEG C of air atmospheres in batch-type furnace,
Take out grinding, then move into Muffle furnace 900 DEG C of calcinings 12 it is small when, calcination stage heating rate is 4 DEG C/min, you can is obtained
Li1.2Mn0.54Ni0.13Co0.13O2(LMNCO) powder.
(2) LiFePO is prepared4The Li of cladding1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Fe=1:1,0.0324gLiCOOCH is weighed respectively3·2H2O and 0.0881gFeSO4·7H2O,
It is dissolved in 40mL deionized waters；By 0.0365gNH4H2PO4(Li:P=1:1) it is dissolved in 10mL deionizations, then by ammonium dihydrogen phosphate
Aqueous solution is slowly dropped into wherein and is stirred continuously, and is subsequently added into the LMNCO powder of 1g steps (1) preparation, is heated to 80 DEG C, with
When the speed sealing magnetic stirring 4 of 180r/min is small, stand 12 it is small when after, with deionized water and absolute ethyl alcohol centrifugal elutriation three times,
Slightly ground after drying, when the lower 400 DEG C of roastings 5 of argon gas flox condition are small in immigration tube furnace, gained covering material is labeled as
LFP-400, the amount of cladding is 5wt%, the LiFePO of cladding4It is crystalline state.
Embodiment 2
(1) Li is prepared1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Mn:Ni:Co is 1.32:0.54:0.13:0.13 ratio measures LiCOOCH3·2H2O, Mn
(COOCH3)2, Ni (COOCH3)2·4H2O, Co (COOCH3)2·4H2O, is dissolved in 100mL deionized waters, it is molten to obtain salt-mixture
Liquid；Then a certain amount of citric acid (citric acid：Metal ion=3:1 molar ratio) it is dissolved in 50mL deionized waters and stirs evenly；
Aqueous citric acid solution is slowly dropped in mixing salt solution, 80 DEG C, when magnetic stirring 4 is small is heated to, it is transparent solidifying to form pink
Glue, when gel is moved into 80 DEG C of dryings 12 are small in air dry oven, when pre-burning 5 is small under 480 DEG C of air atmospheres in batch-type furnace,
Take out grinding, then move into Muffle furnace 900 DEG C of calcinings 12 it is small when, calcination stage heating rate is 4 DEG C/min, you can is obtained
Li1.2Mn0.54Ni0.13Co0.13O2(LMNCO) powder.
(2) LiFePO is prepared4The Li of cladding1.2Mn0.54Ni0.13Co0.13O2
Li in molar ratio:Fe=1:1,0.0324gLiCOOCH is weighed respectively3·2H2O and 0.0881gFeSO4·7H2O,
It is dissolved in 40mL deionized waters；By 0.0365gNH4H2PO4(Li:P=1:1) it is dissolved in 10mL deionizations, then by ammonium dihydrogen phosphate
Aqueous solution is slowly dropped into wherein and is stirred continuously, and is subsequently added into the LMNCO powder of 1g steps (1) preparation, is heated to 80 DEG C, with
When the speed sealing magnetic stirring 5 of 160r/min is small, stand 12 it is small when after, with deionized water and absolute ethyl alcohol centrifugal elutriation three times,
Slightly ground after drying, when the lower 500 DEG C of roastings 5 of argon gas flox condition are small in immigration tube furnace, gained covering material is labeled as
LFP-500, the amount of cladding is 5wt%, the LiFePO of cladding4It is crystalline state.
XRD, SEM of LFP-400 made from pure rich lithium material LMNCO, embodiment 1, LFP-500 made from embodiment 2
With TEM results difference as shown in Figure 1, 2, 3.Electrochemical property test is carried out using 2032 button cells：According to active material：Charcoal
It is black：Poly- (vinylidene fluoride) is 75:15:10 mass ratio is dissolved in N methyl pyrrolidones, is uniformly applied on aluminium foil, 120 DEG C
Positive plate is made after dried overnight.Anode is lithium piece, and membrane is Celgard 2400, and electrolyte is dissolved in EC/ for 1M LiPF6
DMC/DEC(1:1:1in wt.%).The assembling process of battery is completed in glove box.The charge-discharge test of battery is in new prestige CT-
Carried out on 3008.First charge-discharge curve, cycle performance and the high rate performance difference of sample are as shown in Figure 4,5, 6.After cladding
The coulombic efficiency first of sample can reach 91.9%, and specific discharge capacity is up under 0.1C (1C=300mA/g) electric current
295mAh/g.The high rate performance of sample is greatly improved after particularly coating, and 5C multiplying powers discharge capacity can reach
201.8mAh/g, still has 183.8mAh/g, significantly larger than uncoated sample after 50 circulations.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make case study on implementation various modifications, and described herein one
As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here
Example, those skilled in the art disclose according to the present invention, and not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (7)
1. a kind of lithium-rich anode material of LiFePO4 cladding, it is characterised in that including rich lithium material and be coated on rich lithium material
The LiFePO4 on surface, its chemical formula are LiFePO4-Li1.2Mn0.54Ni0.13Co0.13O2, structure is stratiform α-NaFeO2Structure,
The space group of stratiform is RThe mass percent of m, wherein LiFePO4 are 3-7%.
2. the preparation method of the lithium-rich anode material of LiFePO4 as claimed in claim 1 cladding, it is characterised in that including with
Lower step：
（1）Prepare Li1.2Mn0.54Ni0.13Co0.13O2：According to Li:Mn:Ni:The molar ratio of Co is 1.32:0.54:0.13:0.13 claims
Take LiCOOCH3·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH3)2·4H2O, is dissolved in deionized water
In, it is made into mixing salt solution；According to citric acid：Metal ion=3:1, aqueous citric acid solution is added in mixing salt solution, is added
For heat to 80 DEG C, magnetic stirring 4h, forms pink clear gel；Gel is moved into drying in air dry oven, in batch-type furnace
Pre-burning 5h under 480 DEG C of air atmospheres, takes out grinding, then moves into 900 DEG C of calcining 12h in Muffle furnace, is made
Li1.2Mn0.54Ni0.13Co0.13O2Powder；
（2）Prepare the lithium-rich anode material of LiFePO4 cladding：According to molar ratio Li:Fe is 1:1 weighs LiCOOCH respectively3·
2H2O and FeSO4·7 H2O, is dissolved in deionized water, according to molar ratio Li:P=1:1, by NH4H2PO4Aqueous solution is slowly dropped into it
In and be stirred continuously, be subsequently added into step（1）The Li of preparation1.2Mn0.54Ni0.13Co0.13O2Powder, heating sealing magnetic stirring are quiet
Wash after putting 12h, slightly ground after dry, move into tube furnace the 300-500 DEG C of roasting 3-5h under protective atmosphere, phosphoric acid is made
The lithium-rich anode material of iron lithium cladding.
3. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 1, it is characterised in that described
Step（1）Drying temperature is 80 DEG C, drying time 12h.
4. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（1）In 900 DEG C calcining heating rates be 4 DEG C/min.
5. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle heating sealing magnetic, which stirs, is：60-100 DEG C is heated to, magnetic mixing speed is 80-180r/min, preferably mixing speed
160r/min, magnetic mixing time are 3-5h, preferably mixing time 4h.
6. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle washing is to use deionized water and absolute ethyl alcohol centrifugal elutriation three times successively.
7. the preparation method of the lithium-rich anode material of LiFePO4 cladding according to claim 2, it is characterised in that described
Step（2）Middle protective atmosphere is high-purity argon gas.
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| CN114242980A (en) * | 2021-12-16 | 2022-03-25 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate composite material, preparation method and application |
| WO2022109886A1 (en) * | 2020-11-25 | 2022-06-02 | 宁德时代新能源科技股份有限公司 | Composite positive electrode material and preparation method therefor, positive electrode plate, secondary battery and battery module comprising same, battery pack, and device |
| CN114725369A (en) * | 2022-02-10 | 2022-07-08 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
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| CN114725369A (en) * | 2022-02-10 | 2022-07-08 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
| CN116154144A (en) * | 2023-04-24 | 2023-05-23 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, positive electrode plate, battery cell, battery and electric equipment |
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