CN108807918A - A kind of lithium-rich manganese-based anode material and preparation method thereof of surface covered composite yarn - Google Patents
A kind of lithium-rich manganese-based anode material and preparation method thereof of surface covered composite yarn Download PDFInfo
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Abstract
The invention discloses a kind of tungsten oxide β-WO2.9Lithium-rich manganese-based layered cathode material of coated lithium ion battery and preparation method thereof, wherein tungsten oxide include removing β-WO2.9Outside, also a small amount of WO3、WO2.72And WO2Oxide.With lithium-rich manganese-based anode material Li [LixNiyCo1‑x‑y‑zMnz]O2For raw material；Mix simultaneously coating beta-WO2.9.The present invention utilizes tungsten oxide β-WO2.9Unique architectural characteristic has greatly improved to the coulombic efficiency for the first time of anode material for lithium-ion batteries, while improving its electrochemical stability structural stability, significantly improves the cyclical stability of anode material for lithium-ion batteries, and manufacture craft is simple, at low cost.
Description
Technical field
The invention belongs to field of lithium ion battery anode, and in particular to a kind of surface covered composite yarn it is lithium-rich manganese-based just
Pole material and preparation method thereof.
Background technology
Lithium-rich manganese-based anode material shows good application prospect, and theoretical discharge specific capacity reaches 300mAh/g, almost
It is to have been commercialized at present twice or so of positive electrode actual capacity, it is and common while in this material based on Mn elements
Brill acid lithium and nickel bore manganese ternary system anode material and compare, not only price is low, but also safety is good.Therefore, lithium-rich manganese-based anode
Material is considered as the choosing of the ideal of next-generation power lithium-ion battery.But the irreversible capacity for the first time of the material it is high, cycle and
High rate performance is poor, and being pressed in especially discharging during charge and discharge cycles constantly reduces, and hinders its practical application.
Method for coating generally uses one or more of inert substances or conductive material, is formed on the surface of original material
Clad reduces electrode/electrolyte interface impedance, also can reach to protect the surface of original material not corroded by electrolyte
Inhibit oxygen loss and the effect of crystal transition of the lithium-rich manganese-based anode material in cyclic process, therefore using cladding come to richness
Lithium manganese-based anode material be modified processing can play the role of to the raising of the chemical property of material it is larger.Mostly use phosphorus at present
The shortcomings of discharge capacity for the first time of material reduces after hydrochlorate or indifferent oxide are coated as clad, but presence.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide one kind and being coated with β-WO2.9Richness
Lithium manganese-based anode material and preparation method thereof.
Technical scheme is as follows：
A kind of lithium-rich manganese-based anode material of surface covered composite yarn, it is characterised in that：With lithium-rich manganese-based anode material Li
[LixNiyCo1-x-y-zMnz]O2For raw material, wherein：0 < x <, 1,0 < y <, 0.4,0.4 < z < 1, surface is coated with β-WO2.9Material
Expect clad.
Preferably, β-WO2.9Quality be lithium-rich manganese-based anode material Li [LixNiyCo1-x-y-zMnz]O2The 0.5 of quality~
10%.
Preferably, clad also contains a small amount of WO2.72And/or WO3。
The present invention also provides a kind of preparation methods of the lithium-rich manganese-based anode material of surface covered composite yarn, which is characterized in that
Include the following steps：
1) one or more in wolframic acid or tungstates are scattered in ammonia spirit, urea is added after being uniformly dispersed and is made
The aqueous solution of intermediate compound I RT, by raw material lithium-rich manganese-based anode material Li [LixNiyCo1-x-y-zMnz]O2It is water-soluble to be distributed to gained IRT
In liquid, suspension is obtained；
2) after a certain period of time by the suspension freeze-drying in step 1, under ammonia atmosphere, in certain pressure and temperature
Under, through calcining, incubation step, obtains to surface and be coated with β-WO2.9The lithium-rich manganese-based anode material of material.
Preferably, in step 1), the dispersing mode be stirring, stirring condition be at room temperature, mixing speed be 600~
900r/min stirs 20~40min.
Preferably, in step 2), the time of freeze-drying is 48~72h, it is preferable that under ammonia atmosphere, gas in boiler tube
Body pressure controls between 5~10mm water columns of atmospheric pressure, calcines 5~6h under the conditions of 450~550 DEG C, then 550~
5~6h is kept the temperature at 650 DEG C.
Preferably, the tungstates is the one or two of ammonium tungstate or ammonium metatungstate.
The present invention also provides a kind of table lithium-rich manganese-based anode material Li [LixNiyCo1-x-y-zMnz]O2Preparation method, it is described
Preparation method includes the following steps：
A) manganese salt, brill salt and nickel salt are scattered in deionized water, under conditions of mixing speed is 600~900r/min,
Stir 1~3h；Wherein metal ion total concentration is 2mol/L；
B) under conditions of low whipping speed is 600~900r/min, ammonium hydrogen carbonate is added into the solution obtained by step a)
Solution and sodium carbonate liquor, then proceed to 2~4h of stirring to react complete；With ethyl alcohol and deionized water centrifugation, washing and dry,
Obtain carbonate precursor；Wherein a concentration of 1.5~6mol/L of ammonium bicarbonate soln and sal volatile；
C) presoma obtained by step b) is sufficiently mixed with lithium source, then mixture is put into tube furnace, 400
5~6h is calcined at~500 DEG C, is calcined 14~18h at latter persistently overheating to 800~950 DEG C, is obtained lithium-rich manganese-based stratified material,
It is 1: 1.50~1.59 that nickel, which bores manganese integral molar quantity and the mole ratio of lithium,.
Preferably, the lithium source is one or more of lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide；Institute
It is one or more of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate to state manganese salt；The nickel salt is nickel nitrate, acetic acid
One or more of nickel, nickel chloride or nickel sulfate；The brill salt is that nitric acid bores, in acetic acid brill, Cobalt Chloride or sulfuric acid brill
One or more.
Tungsten oxide β-the WO that technical solution of the present invention obtains2.9Due to its unique defects, can provide more
Embedding lithium vacancy, to further increase the specific discharge capacity of lithium-rich manganese-based anode material.After coating modification it is lithium-rich manganese-based just
Pole material is applied in lithium ion battery, and the performance of lithium ion battery is significantly increased at room temperature, and charging/discharging voltage is ranging from
2.0~4.6V, charging and discharging currents 20mA/g, up to 87.43% or more, first discharge specific capacity reaches coulombic efficiency for the first time
290mAh/g or more.The capacity retention ratio of 100 circle of cycle is up to 86.78% or more under the current density of 200mA/g.
Compared with the prior art, the advantages of the present invention are as follows：
1) lithium-rich manganese-based anode material of surface covered composite yarn produced by the present invention have specific capacity height, good rate capability,
The advantages that having extended cycle life.
2) preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn of the invention is easy to operate, environmental friendly,
Controllability and favorable reproducibility are suitble to large-scale production.
Description of the drawings
The present invention is described in further details in the following with reference to the drawings and specific embodiments.
Fig. 1 is the scanning electron microscope (SEM) photograph of lithium-rich manganese-based anode material presoma prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of lithium-rich manganese-based anode material prepared by the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the lithium-rich manganese-based anode material of surface covered composite yarn prepared by the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope picture of the lithium-rich manganese-based anode material of surface covered composite yarn prepared by the embodiment of the present invention 1.
Fig. 5 is prepared by the lithium-rich manganese-based anode material of surface covered composite yarn prepared by the embodiment of the present invention 1 and comparative example 1
Lithium-rich manganese-based anode material XRD curve comparison figures.
Fig. 6 is prepared by the lithium-rich manganese-based anode material of surface covered composite yarn prepared by the embodiment of the present invention 2 and comparative example
Lithium-rich manganese-based anode material the first charge-discharge curve comparison figure of lithium ion battery is made.
Fig. 7 is prepared by the lithium-rich manganese-based anode material of surface covered composite yarn prepared by the embodiment of the present invention 3 and comparative example
Lithium-rich manganese-based anode material the cycle performance curve comparison figure of lithium ion battery is made.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from well known method.
Embodiment 1：
It is Li [Li that a kind of lithium-rich manganese-based anode material of surface covered composite yarn, which is in chemical formula,0.2Mn0.54Ni0.13Co0.13]
O2Layer structure lithium-rich manganese-based anode material outer surface coating beta-WO2.9；In embodiment 1, covering amount β-WO2.9/Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 1%.
The preparation method of the lithium-rich manganese-based anode material of above-mentioned surface covered composite yarn the specific steps are：
(1) MnSO is weighed at Mn: Ni: Co=0.54: 0.13: 0.13 in molar ratio4·H2O, NiSO4·6H2O and CoSO4·
7H2O is scattered in deionized water, and the NH of 4mol/L is added after disperseing completely4HCO3The Na of solution and 1.5mol/L2CO3Solution fills
Stirring to reaction is divided to complete.By obtained persursor material and excessive Li2CO3Be fully ground in mortar, be put into crucible into
Row heat treatment, first keeps the temperature 6h at 500 DEG C, and 16h (heating rate is 5 DEG C/min) is then kept the temperature at 900 DEG C to get to richness
Lithium manganese-based anode material obtains Mn0.54Ni0.13Co0.13(CO3)0.8Presoma.Weigh the Mn of 5g0.54Ni0.13Co0.13(CO3)0.8Before
Drive the pure Li of analysis of body and 2.370g2CO3It is fully ground in mortar.Obtaining element group becomes Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Mixture.As shown in Figure 1, being Mn manufactured in the present embodiment0.54Ni0.13Co0.13(CO3)0.8
The scanning electron microscope (SEM) photograph of presoma, as can be seen from the figure the presentation of gained presoma is spherical, and diameter is about 10~20 μm or so, shape
Shape is more uniform, and surface is relatively smooth.
(2) powder that step 1 obtains is put into crucible and is heat-treated, heat treatment parameter is first warming up to 5 DEG C/min
500 DEG C of heat preservation 6h, are then continuously heating to 900 DEG C with 5 DEG C/min again, keep the temperature 16h, the thinner richness of granularity is obtained after furnace cooling
Lithium manganese base layered cathode material Li [Li0.2Mn0.54Ni0.13Co0.13]O2.As shown in Fig. 2, the Li obtained for the present embodiment
[Li0.2Mn0.54Ni0.13Co0.13]O2Scanning electron microscope (SEM) photograph, as can be seen from the figure gained stratified material is spherical shape, and diameter is about 10 μ
M or so, shapes and sizes are more uniform.
(3) β-WO are pressed2.9/Li[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 1%, weigh (the NH of 10.68mg4)6H2W12O40·xH2O is scattered in 1molL-1Ammonia spirit in, after being uniformly dispersed be added 25.90mg urea, be configured to 20mL's
Intermediate compound I RT aqueous solutions weigh positive electrode made from 1g steps (2) and are scattered in IRT aqueous solutions, are stirred at room temperature
30min obtains the suspension of tungsten oxide and lithium-rich manganese-based layered cathode material；
(4) it by after slurry freeze-drying 48h obtained by step (3), is placed in tube furnace, under ammonia atmosphere, gas in boiler tube
6h is calcined in the control of body pressure under the conditions of the 10mm water columns with atmospheric pressure, 450 DEG C, then keeps the temperature at 650 DEG C 6h to get to β-
WO2.9The lithium-rich manganese-based anode material of cladding, as shown in figure 3, for surface covered composite yarn manufactured in the present embodiment it is lithium-rich manganese-based just
The scanning electron microscope (SEM) photograph of pole material, it can be seen from the figure that after surface coats, the surface of material becomes more smooth.Such as Fig. 4
It is shown, it is the transmission electron microscope picture of the lithium-rich manganese-based anode material of surface covered composite yarn manufactured in the present embodiment, as seen from the figure, β-
WO2.9Uniformly it is wrapped in lithium-rich manganese-based layered cathode material, while also a small amount of WO2.72、WO3、WO2It is coated on material surface, is wrapped
Coating thickness is about 20nm or so.
The lithium-rich manganese-based anode material of the surface covered composite yarn of the present embodiment is subjected to X-ray diffraction test, XRD curves
As shown in (b) curve in Fig. 5, related data is as shown in table 1.By analyze XRD data it is found that cladding after material peak intensity
Without significant change, but there are β-WO in treated material2.9And WO2.72The peak of equal tungsten oxides, illustrates β-WO2.9Success
Ground is coated on material surface.Meanwhile after processing material a values and c values without significant change, but I (003)/I (104) value has significantly
Ground increases, and illustrates that the layer structure of material after coating more is stablized and ion mixing is more uniform.
Embodiment 2：
It is Li [Li that a kind of lithium-rich manganese-based anode material of surface covered composite yarn, which is in chemical formula,0.2Mn0.54Ni0.13Co0.13]
O2Layer structure lithium-rich manganese-based anode material outer surface coating beta-WO2.9；In example 2, covering amount β-WO2.9/Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 3%.
The preparation method of the lithium-rich manganese-based anode material of above-mentioned surface covered composite yarn the specific steps are：
(1) MnSO is weighed at Mn: Ni: Co=0.54: 0.13: 0.13 in molar ratio4·H2O, NiSO4·6H2O and CoSO4·
7H2O is scattered in deionized water, and the NH of 6mol/L is added after disperseing completely4HCO3The Na of solution and 3mol/L2CO3Solution, fully
Stirring to reaction is completed.By obtained persursor material and excessive Li2CO3It is fully ground in mortar, is put into crucible and carries out
Heat treatment first keeps the temperature 6h at 500 DEG C, and 16h (heating rate is 5 DEG C/min) is then kept the temperature at 900 DEG C to get to rich lithium
Manganese-based anode material obtains Mn0.54Ni0.13Co0.13(CO3) 0.8 presoma.Weigh the Mn of 5g0.54Ni0.13Co0.13(CO3)0.8Forerunner
The pure Li2CO3 of analysis of body and 2.370g are fully ground in mortar.Obtaining element group becomes Li [Li0.2Mn0.54Ni0.13Co0.13]
O2Mixture.
(2) powder that step 1 obtains is put into crucible and is heat-treated, heat treatment parameter is first warming up to 5 DEG C/min
450 DEG C of heat preservation 6h, are then continuously heating to 900 DEG C with 5 DEG C/min again, keep the temperature 16h, the thinner richness of granularity is obtained after furnace cooling
Lithium manganese base layered cathode material Li [Li0.2Mn0.54Ni0.13Co0.13]O2。
(3) β-WO are pressed2.9/Li[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 3%, weigh the H of 32.32mg2WO4Point
It dissipates in 1molL-1Ammonia spirit in, after being uniformly dispersed be added 77.70mg urea, be configured to the intermediate compound I RT aqueous solutions of 20mL,
It weighs positive electrode made from 1g steps (2) to be scattered in IRT aqueous solutions, ultrasonic 60min obtains β-WO2.9With lithium-rich manganese-based layer
The suspension of shape positive electrode；
(4) it by after slurry freeze-drying 72h obtained by step (3), is placed in tube furnace, under ammonia atmosphere, gas in boiler tube
The control of body pressure calcines 6h in the 8mm water columns with atmospheric pressure under the conditions of 500 DEG C, then keep the temperature at 650 DEG C 6h to get to
β-WO2.9The lithium-rich manganese-based anode material of cladding,
Lithium ion battery is made in the lithium-rich manganese-based anode material of the surface covered composite yarn of the present embodiment, electrification is carried out to it
Shown in figure (b) in performance test, first charge-discharge curve such as Fig. 6.From figure it can be found that modified material for the first time
Irreversible capacity is reduced to 44.98mAh/g, the coulombic efficiency for the first time of material to be increased to from 74.62% from 85.85mAh/g
87.43%, at the same time, discharge capacity increases to 305.86mAh/g from 252.40mAh/g for the first time, illustrates β-WO2.9Clad
Due to the particularity of its structure, vacancy of more holes as lithium ion insertion and deintercalation in charge and discharge process can be provided,
The migration rate for improving lithium ion in lithium ion battery reduces irreversible appearance for the first time to significantly improve the first charge discharge efficiency of material
Amount loss.
Embodiment 3：
It is Li [Li that a kind of lithium-rich manganese-based anode material of surface covered composite yarn, which is in chemical formula,0.2Mn0.54Ni0.13Co0.13]
O2Layer structure lithium-rich manganese-based anode material outer surface coating beta-WO2.9；In embodiment 3, covering amount β-WO2.9/Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 5%.
The preparation method of the lithium-rich manganese-based anode material of above-mentioned surface covered composite yarn the specific steps are：
It is Li [Li that a kind of lithium-rich manganese-based anode material of surface covered composite yarn, which is in chemical formula,0.2Mn0.54Ni0.13Co0.13]
O2Layer structure lithium-rich manganese-based anode material outer surface coating beta-WO2.9；In embodiment 3, covering amount β-WO2.9/Li
[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 5%.
The preparation method of the lithium-rich manganese-based anode material of above-mentioned surface covered composite yarn the specific steps are：
(1) MnSO is weighed at Mn: Ni: Co=0.54: 0.13: 0.13 in molar ratio4·H2O, NiSO4·6H2O and CoSO4·
7H2O is scattered in deionized water, and the NH of 6mol/L is added after disperseing completely4HCO3The Na of solution and 3mol/L2CO3Solution, fully
Stirring to reaction is completed.By obtained persursor material and excessive Li2CO3It is fully ground in mortar, is put into crucible and carries out
Heat treatment first keeps the temperature 6h at 500 DEG C, and 16h (heating rate is 5 DEG C/min) is then kept the temperature at 900 DEG C to get to rich lithium
Manganese-based anode material obtains Mn0.54Ni0.13Co0.13(CO3)0.8Presoma.Weigh the Mn of 5g0.54Ni0.13Co0.13(CO3)0.8Forerunner
The pure Li of analysis of body and 2.370g2CO3It is fully ground in mortar.Obtaining element group becomes Li [Li0.2Mn0.54Ni0.13Co0.13]
O2Mixture.
(2) powder that step 1 obtains is put into crucible and is heat-treated, heat treatment parameter is first warming up to 5 DEG C/min
500 DEG C of heat preservation 6h, are then continuously heating to 900 DEG C with 5 DEG C/min again, keep the temperature 16h, the thinner richness of granularity is obtained after furnace cooling
Lithium manganese base layered cathode material Li [Li0.2Mn0.54Ni0.13Co0.13]O2。
(3) β-WO are pressed2.9/Li[Li0.2Mn0.54Ni0.13Co0.13]O2Mass ratio be 5%, weigh (the NH of 53.39mg4)6H2W12O40·xH2O is scattered in 1molL-1Ammonia spirit in, after being uniformly dispersed be added 129.50mg urea, be configured to 20mL's
Intermediate compound I RT aqueous solutions weigh positive electrode made from 1g steps (2) and are scattered in IRT aqueous solutions, and ultrasonic 60min obtains β-
WO2.9With the suspension of lithium-rich manganese-based layered cathode material；
(4) it by after slurry freeze-drying 72h obtained by step (3), is placed in tube furnace, under ammonia atmosphere, gas in boiler tube
The control of body pressure calcines 6h in the 8mm water columns with atmospheric pressure under the conditions of 550 DEG C, then keep the temperature at 600 DEG C 6h to get to
β-WO2.9The lithium-rich manganese-based anode material of cladding,
Lithium ion battery is made in the lithium-rich manganese-based anode material of the surface covered composite yarn of the present embodiment, performance is carried out to it
Test recycles 100 circles shown in the curve (b) under high current density (0.5C) in cycle performance such as Fig. 7 under 0.5C, material
First discharge specific capacity is 260.01mAh/g, and the cyclical stability of capacity retention ratio 86.78%, material is preferable, β-WO2.9Packet
Coating is effectively improved the structural stability and chemical property of lithium-rich manganese-based anode material.
Comparative example：
(1) lithium-rich manganese-based anode material is prepared：Weigh MnSO at Mn: Ni: Co=0.54: 0.13: 0.13 in molar ratio4·
H2O, NiSO4·6H2O and CoSO4·7H2O is scattered in deionized water, and the NH of 4mol/L is added after disperseing completely4HCO3Solution
With the Na of 1.5mol/L2CO3Solution is stirred well to reaction and completes.By obtained persursor material and excessive Li2CO3Yu Yan
It is fully ground in alms bowl, is put into crucible and is heat-treated, first keep the temperature 6h at 500 DEG C, 16h (heatings are then kept the temperature at 900 DEG C
Rate is 5 DEG C/min) obtain Mn to get to lithium-rich manganese-based anode material0.54Ni0.13Co0.13(CO3)0.8Presoma.Weigh 5g
Mn0.54Ni0.13Co0.13(CO3)0.8The pure Li of analysis of presoma and 2.370g2CO3It is fully ground in mortar.Obtain element group
As Li [Li0.2Mn0.54Ni0.13Co0.13]O2Mixture.
(2) it is sintered：The powder that step 1 obtains is put into crucible and is heat-treated, heat treatment parameter is first with 5 DEG C/min liters
Then temperature is continuously heating to 900 DEG C with 5 DEG C/min again, keeps the temperature 16h, it is thinner to obtain granularity after furnace cooling to 500 DEG C of heat preservation 6h
Lithium-rich manganese-based layered cathode material Li [Li0.2Mn0.54Ni0.13Co0.13]O2。
The lithium-rich manganese-based anode material of this comparative example is subjected to X-ray diffraction test, (a) in XRD curves such as Fig. 5 is bent
Shown in line, related data is as shown in table 1.By analysis XRD data it is found that its I (003)/I (104) value is relatively low, illustrate to coat
The layer structure of preceding material and ion mixing are poor.Lithium ion battery pair is made in the lithium-rich manganese-based anode material of this comparative example
Shown in figure (a) in its progress electrochemical property test, first charge-discharge curve such as Fig. 6, the appearance irreversible for the first time of raw material
Amount is up to 85.85mAh/g, and coulombic efficiency is only 74.62% for the first time, and irreversible capacity is larger for the first time.Its high current density
Shown in curve (a) under (0.5C) in cycle performance such as Fig. 7, the capacity retention ratio of material is poor, and 100 circles, material are recycled under 0.5C
The first discharge specific capacity of material is 237.01mAh/g, but capacity retention ratio is only 23.63%, and the cyclical stability of material is poor.
Above example is one kind of the present invention more preferably specific implementation method, and those skilled in the art are in the technical program
The usual variations and alternatives carried out in range should be included within the scope of the present invention.
Claims (9)
1. a kind of lithium-rich manganese-based anode material of surface covered composite yarn, it is characterised in that：With lithium-rich manganese-based anode material Li
[LixNiyCo1-x-y-zMnz]O2For raw material, wherein：0<x<1,0<y<0.4,0.4<z<1, surface is coated with β-WO2.9Material coats
Layer.
2. a kind of lithium-rich manganese-based anode material of surface covered composite yarn as described in claim 1, it is characterised in that：β-WO2.9's
Quality is lithium-rich manganese-based anode material Li [LixNiyCo1-x-y-zMnz]O2The 0.5~10% of quality.
3. a kind of lithium-rich manganese-based anode material of surface covered composite yarn as described in claim 1, it is characterised in that：Clad is also
Contain a certain amount of WO2.72、WO2And/or WO3。
4. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as described in claim 1-3, feature
It is, includes the following steps：
1）One or more in wolframic acid or tungstates are scattered in ammonia spirit, urea is added after being uniformly dispersed and is made intermediate
The aqueous solution of body IRT, by raw material lithium-rich manganese-based anode material Li [LixNiyCo1-x-y-zMnz]O2It is distributed to gained IRT aqueous solutions
In, obtain suspension；
2）After a certain period of time by the suspension freeze-drying in step 1, under ammonia atmosphere, under certain pressure and temperature,
Through calcining, incubation step, obtains to surface and be coated with β-WO2.9The lithium-rich manganese-based anode material of material.
5. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as claimed in claim 4, feature exist
In step 1）In, the dispersing mode is stirring, and stirring condition is that at room temperature, mixing speed is 600~900r/min, stirring
20~40min.
6. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as claimed in claim 4, feature exist
In step 2）In, the time of freeze-drying is 48~72 h, it is preferable that gas pressure, which controls, under ammonia atmosphere, in boiler tube exists
Between 5~10 mm water columns of atmospheric pressure, 5~6h is calcined under the conditions of 450~550 DEG C, then kept the temperature at 550~650 DEG C
5~6 h.
7. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as claimed in claim 4, feature exist
In the tungstates is the one or two of ammonium tungstate or ammonium metatungstate.
8. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as claimed in claim 4, feature exist
In the preparation method of the raw material includes the following steps：
a）Manganese salt, cobalt salt and nickel salt are scattered in deionized water, under conditions of mixing speed is 600~900r/min, stirring 1
~3h；Wherein metal ion total concentration is 2 mol/L；
b）Under conditions of low whipping speed is 600~900r/min, to step a）Ammonium bicarbonate soln is added in the solution of gained
And sodium carbonate liquor, then proceed to 2~4 h of stirring to react complete；With ethyl alcohol and deionized water centrifugation, washing and drying, obtain
To carbonate precursor；Wherein a concentration of 1.5~6mol/L of ammonium bicarbonate soln and sal volatile；
c）By step b）Gained presoma is sufficiently mixed with lithium source, and then mixture is put into tube furnace, 400~
5~6h is calcined at 500 DEG C, is calcined 14~18h at latter persistently overheating to 800~950 DEG C, is obtained lithium-rich manganese-based stratified material, nickel
The mole ratio of cobalt manganese integral molar quantity and lithium is 1:1.50~1.59.
9. a kind of preparation method of the lithium-rich manganese-based anode material of surface covered composite yarn as claimed in claim 8, feature exist
In the lithium source is one or more of lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide；The manganese salt is nitric acid
One or more of manganese, manganese acetate, manganese chloride or manganese sulfate；The nickel salt is nickel nitrate, nickel acetate, nickel chloride or sulphur
One or more of sour nickel；The cobalt salt be one or both of cobalt nitrate, cobalt acetate, cobalt chloride or cobaltous sulfate with
On.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111211302A (en) * | 2020-01-10 | 2020-05-29 | 桑顿新能源科技有限公司 | Lithium ion battery anode material and preparation method thereof, lithium ion battery anode, lithium ion battery and power utilization equipment |
| CN114039031A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Tungsten single-coating anode material and preparation method and application thereof |
| CN114400314A (en) * | 2022-01-07 | 2022-04-26 | 浙江大学衢州研究院 | Surface reconstruction-based ternary cathode material of lithium ion battery and preparation method thereof |
| CN114447290A (en) * | 2021-12-21 | 2022-05-06 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN114597368A (en) * | 2022-03-15 | 2022-06-07 | 北京理工大学 | Surface sulfur-doped lithium-rich manganese-based layered material with lithium sulfate protective layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
| CN105051950A (en) * | 2013-03-15 | 2015-11-11 | 株式会社东芝 | Electrode material for batteries, substrate for batteries using same, storage battery, dye-sensitized solar cell, capacitor and li ion secondary battery |
| KR20160050835A (en) * | 2014-10-31 | 2016-05-11 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery, and cathode and lithium secondary battery comprising the same |
| CN106688129A (en) * | 2014-09-11 | 2017-05-17 | 株式会社东芝 | Electrode material, and electrode layer, battery and electrochromic element each of which uses same |
-
2018
- 2018-06-15 CN CN201810623442.XA patent/CN108807918B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105051950A (en) * | 2013-03-15 | 2015-11-11 | 株式会社东芝 | Electrode material for batteries, substrate for batteries using same, storage battery, dye-sensitized solar cell, capacitor and li ion secondary battery |
| CN106688129A (en) * | 2014-09-11 | 2017-05-17 | 株式会社东芝 | Electrode material, and electrode layer, battery and electrochromic element each of which uses same |
| KR20160050835A (en) * | 2014-10-31 | 2016-05-11 | 주식회사 엘지화학 | Cathode active material for lithium secondary battery, and cathode and lithium secondary battery comprising the same |
| CN104961159A (en) * | 2015-07-09 | 2015-10-07 | 华东理工大学 | Nano-tungsten oxide, one-step vapor phase reduction preparation method of nano-tungsten oxide and application of nano-tungsten oxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111211302A (en) * | 2020-01-10 | 2020-05-29 | 桑顿新能源科技有限公司 | Lithium ion battery anode material and preparation method thereof, lithium ion battery anode, lithium ion battery and power utilization equipment |
| CN114039031A (en) * | 2021-11-02 | 2022-02-11 | 远景动力技术(江苏)有限公司 | Tungsten single-coating anode material and preparation method and application thereof |
| CN114447290A (en) * | 2021-12-21 | 2022-05-06 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN114447290B (en) * | 2021-12-21 | 2023-04-11 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
| CN114400314A (en) * | 2022-01-07 | 2022-04-26 | 浙江大学衢州研究院 | Surface reconstruction-based ternary cathode material of lithium ion battery and preparation method thereof |
| CN114597368A (en) * | 2022-03-15 | 2022-06-07 | 北京理工大学 | Surface sulfur-doped lithium-rich manganese-based layered material with lithium sulfate protective layer |
| CN114597368B (en) * | 2022-03-15 | 2023-10-31 | 北京理工大学 | Lithium-rich manganese-based layered material with surface sulfur doped and lithium sulfate protective layer |
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