CN108767254A - A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material - Google Patents
A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material Download PDFInfo
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Abstract
The invention discloses a kind of surface texture of stratiform lithium-rich anode material and chemical composition synchronization modulation method, the general formula of the positive electrode is：xLi2MnO3·(1‑x)LiMO2Or Li1+x[M]1‑xO2, one or more of M Mn, Co, Ni；Include the following steps：1）Carbonate precursor is placed in processing agent solution and is surface-treated；2）By treated, carbonate precursor is burnt into oxide, then is uniformly mixed with Li source compound, and the stratiform lithium-rich anode material of surface modification is obtained by high-temperature calcination.The main body of the material is layer structure, and surface is Spinel, is transition mixed phase between layer structure and Spinel, and the chemical composition on surface is different from the chemical composition of main body.The present invention is easy to operate easily-controllable, can assign the superior chemical properties such as the quick lithium ion diffusion admittance of positive electrode, the cycle life of stabilization and faint voltage decay.
Description
Technical field
The present invention relates to a kind of surface textures of stratiform lithium-rich anode material and chemical composition synchronization modulation method, belong to energy
Source material and electrochemical field.
Background technology
Lithium ion battery becomes mesh due to having many advantages, such as that bigger than energy, operating voltage is high, self-discharge rate is low and light weight
The preceding most commonly used power supply system of development and application.However, the energy density of current lithium ion battery, power characteristic, safety
Energy and cost problem, which still restrict its, further to be developed, and is especially difficult to meet the strategic emerging industries such as electric vehicle to height
The application demand of energy density power supply.The energy density of lithium ion battery depends primarily on positive electrode, and improves positive electrode
Specific capacity or operating voltage be obtain high-energy density main path.Compared with Carbon anode specific capacity (~350mAh/g),
The positive electrode of Current commercial, such as stratiform cobalt acid lithium, ternary material, lithium manganate having spinel structure and olivine-type LiFePO4,
All exist specific discharge capacity it is relatively low (<200mAh/g) the problem of.Therefore, of new generation positive electrode of the exploitation with high power capacity, from
And the lithium ion battery for obtaining high-energy density be market apply and industry development active demand.
In the positive electrode currently developed, stratiform lithium-rich anode material xLi2MnO3·(1-x)LiMO2Or Li1+xM1- xO2(transition metal such as M Mn, Ni, Co, 0<x<1) due to height ratio capacity (>250mAh/g), compared with high working voltage, it is low at
Originally extensive research boom at home and abroad and the features such as environmental-friendly is started, is had a extensive future.It is generally believed that the material is layer
Shape Li2MnO3(space group C2/m) and stratiform LiMO2Solid solution that (space group R3m) is formed or both is in nano-scale
It is upper compound.However, the material has the problems such as irreversible capacity is big for the first time, high rate performance is insufficient and voltage decay is serious, hinder
It is commercialized process.The surface nature of stratiform lithium-rich anode material, as surface texture and surface chemistry form, it is considered to be influence
The key factor of chemical property.Common surface modifying method, such as surface cladding, surface doping, acid processing, although can be with
It is effective to improve the performance of material, but often can only individually change in a certain respect, more excellent comprehensive electricity can not be obtained in this way
Chemical property.How to change simultaneously material surface structure or chemical composition still has huge challenge.Therefore, it finds a kind of
Simple controllable method, realizes the synchronization modulation of material surface structure and chemical composition, and height ratio capacity, good is had both to obtain
The positive electrode of high rate performance, excellent capacity and voltage stability has the fast development of lithium ion battery and related industry
Important practical significance.
Invention content
In order to solve the above technical problem, the present invention provides a kind of easy to operate easily-controllable, it is quick positive electrode can be assigned
Lithium ion diffusion admittance, stabilization cycle life and the superior chemical property such as faint voltage decay lithium ion battery layer
Shape lithium-rich anode material surface texture and chemical composition synchronization modulation method.
The technical solution adopted by the present invention is：A kind of surface texture and the same step of chemical composition of stratiform lithium-rich anode material
The general formula of prosecutor method, the stratiform lithium-rich anode material is：xLi2MnO3·(1-x)LiMO2Or Li1+x[M]1-xO2, M in formula
For one or more of transient metal Mn, Co, Ni, 0<x<1；The main body of the stratiform lithium-rich anode material particle is stratiform knot
Structure, surface are Spinel, are transition mixed phase between layer structure and Spinel, and the chemical composition on surface and main body
Chemical composition is different, includes the following steps：
(1) carbonate precursor is placed in processing agent solution, after uniform stirring processing, is washed with distilled water, filters, does
It is dry, the carbonate precursor that obtains that treated；
It (2) will treated that carbonate precursor calcines 4-8h at 400-600 DEG C obtains oxide；The oxygen that will be obtained again
Compound is uniformly mixed by the ratio between molal quantity of lithium and transition metal total mole number for 1.1~1.55 with Li source compound；It will
Obtained mixture calcines 8-24h at 700-900 DEG C, obtains the stratiform lithium-rich anode material of surface modification.
In the surface texture and chemical composition synchronization modulation method of above-mentioned stratiform lithium-rich anode material, the place in step 1)
Reason agent includes one kind or several in ammonium hydroxide, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium nitrate, ammonium acetate or ethylenediamine
The salt-mixture of kind.
In the surface texture and chemical composition synchronization modulation method of above-mentioned stratiform lithium-rich anode material, stirring in step 1)
Mode is using magnetic agitation or mechanical agitation.
In the surface texture and chemical composition synchronization modulation method of above-mentioned stratiform lithium-rich anode material, described in step 2)
Li source compound include one or more of lithium carbonate, lithium hydroxide or lithium nitrate mixture.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is surface-treated carbonate precursor using processing agent solution, based on inorganic agent and metal ion
Complexation reaction, changes the surface chemistry composition of presoma, and the stratiform that surface modification is obtained using high temperature solid-state lithiation is rich
Lithium anode material；The main body of the stratiform lithium-rich anode material is layer structure, and surface is Spinel, gradient mistake between two-phase
It crosses, and surface chemistry composition is different from the chemical composition of main body；The present invention realizes the surface texture of synchronization modulation positive electrode
And chemical constituent, obtained special surface assign the quick lithium ion diffusion admittance of positive electrode, stabilization cycle life and
The superior chemical property such as faint voltage decay；In addition, the present invention is easy to operate easily-controllable, extensive industrialization can be carried out, is had
There is good application prospect.
Description of the drawings
Fig. 1 is the flow chart of the present invention.
Fig. 2 is the carbonate precursor and untreated carbonate precursor obtained by AMMONIA TREATMENT different time of the present invention
SEM schemes：(a) the SEM figures of untreated carbonate precursor, (b) the SEM figures of AMMONIA TREATMENT 5min carbonate precursors, (c) ammonia
The SEM of water process 10min carbonate precursors schemes, (c) the SEM figures of AMMONIA TREATMENT 20min carbonate precursors, (e) at ammonium hydroxide
Manage the SEM figures of 40min carbonate precursors.
Fig. 3 is the carbonate precursor and untreated carbonate precursor obtained by AMMONIA TREATMENT different time of the present invention
EDX energy spectrum diagrams：(a) EDX energy spectrum diagrams of untreated carbonate precursor, (b) carbonate precursor of AMMONIA TREATMENT 10min
EDX energy spectrum diagrams.
Fig. 4 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the SEM figures of stratiform lithium-rich anode material：(a) the SEM figures of stratiform lithium-rich anode material obtained by comparative example, (b) AMMONIA TREATMENT
The SEM figures of stratiform lithium-rich anode material obtained by 5min, (c) the SEM figures of stratiform lithium-rich anode material obtained by AMMONIA TREATMENT 10min,
(d) the SEM figures of stratiform lithium-rich anode material obtained by AMMONIA TREATMENT 20min, (e) stratiform lithium-rich anode obtained by AMMONIA TREATMENT 40min
The SEM of material schemes.
Fig. 5 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the linear scan EDX energy spectrum diagrams of stratiform lithium-rich anode material：(a) gained stratiform lithium-rich anode material after being AMMONIA TREATMENT 10min
The EDX energy spectrum diagrams of material are (b) the EDX energy spectrum diagrams of stratiform lithium-rich anode material obtained by comparative example.
Fig. 6 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the XRD diagram of stratiform lithium-rich anode material.
Fig. 7 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the TEM figures of stratiform lithium-rich anode material：(a) the TEM figures of stratiform lithium-rich anode material obtained by comparative example, (b) AMMONIA TREATMENT
The TEM figures of stratiform lithium-rich anode material obtained by 10min, (c) TEM of box a-quadrant schemes in figure b.
Fig. 8 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the first charge-discharge curve of stratiform lithium-rich anode material.
Fig. 9 is stratiform lithium-rich anode material and comparative example institute obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Obtain the chemical property figure of stratiform lithium-rich anode material：(a) cycle life figure, (b) mean voltage cycle figure, (c) comparative example institute
Stratiform lithium-rich anode material difference cycle-index charging and discharging curve figure, (d) the stratiform richness lithium obtained by AMMONIA TREATMENT 10min is being just
Pole material difference cycle-index charging and discharging curve figure.
Figure 10 is stratiform lithium-rich anode material and comparative example obtained by AMMONIA TREATMENT carbonate precursor different time of the present invention
Gained stratiform lithium-rich anode material high rate performance figure.
Specific implementation mode
Comparative example
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, 500
6h is burnt at DEG C, obtains oxide precursor.
(2) oxide precursor for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio mixing is equal
Even ([Li] is the molal quantity of lithium, and [M] is the total molal quantity of Mn, Ni and Co metal), is subsequently placed in Muffle furnace and is forged at 750 DEG C
12h is burnt, the stratiform lithium-rich anode material in comparative example is obtained, is labeled as LMNC.
Embodiment 1
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ammonia spirit for measuring 30mL3.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
10min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, obtains ammonium hydroxide
Treated carbonate precursor.In order to compare, using same method, time for changing AMMONIA TREATMENT is 5min, 20min and
40min respectively obtains corresponding treated carbonate precursor.
(2) carbonate precursor of AMMONIA TREATMENT 5min, 10min, 20min, 40min for being obtained in step (1) are distinguished
6h is burnt at 500 DEG C, obtains oxide.
(3) oxide for obtaining above-mentioned steps is respectively with lithium carbonate with [Li]:[M]=1.42:1 ratio is uniformly mixed
([Li] is the molal quantity of lithium, and [M] is the molal quantity of the total metal of Mn, Ni and Co), is placed in Muffle furnace and calcines 12h at 750 DEG C,
Obtain the stratiform lithium-rich anode material of surface modification.It is obtained corresponding with AMMONIA TREATMENT 5min, 10min, 20min and 40min
Surface be modified stratiform lithium-rich anode material be respectively labeled as LMNC5, LMNC10, LMNC20 and LMNC40.
SEM tests, as shown in Fig. 2 (a), untreatment carbon hydrochlorate are carried out to untreated and AMMONIA TREATMENT carbonate precursor
Presoma is spheric granules, and size is 2 μm or so, and surface is relatively smooth, as shown in Fig. 2 (b), (c), using AMMONIA TREATMENT 5min
With the presoma of 10min, granule-morphology is similar with untreated samples, and larger change does not occur.However, such as Fig. 2
(d), shown in (e), granular precursor obtained by AMMONIA TREATMENT 20min and 40min, there is different degrees of erosion in surface, and goes out
Existing floccule, while spheric granules illustrates that AMMONIA TREATMENT overlong time, ammonium hydroxide occur with carbonate precursor surface by breakage
It largely chemically reacts, destroys its surface topography.In addition, tested by EDX power spectrums, as shown in Fig. 3 (a), untreated sample
Product surface chemistry forms the Mn that (molar ratio) is 60.73%, 20.06% Ni and 19.21% Co, Mn, Ni, Co three's
Molar ratio and theoretical calculation (3:1:1), and by the sample after AMMONIA TREATMENT 10min, as shown in Fig. 3 (b), the Ni on surface
Constituent content is substantially reduced, about 14.62% (molar ratio), while the content of Mn and Co slightly increases, and illustrates ammonium hydroxide and Ni
Complexation reaction ratio and Mn and Co it is more strong, pass through after ammonium hydroxide proper treatment can be changed surface chemical composition.
The microscopic appearance of the stratiform lithium-rich anode material obtained by high temperature solid-state lithiation is as shown in Figure 4.Such as Fig. 4
(a), (b), (c) are shown, and tri- kinds of positive electrode granule-morphologies of LMNC, LMNC5 and LMNC10 are more similar, keep the ball of presoma
Shape shape, while the primary particle on surface significantly increases, and illustrates that crystallinity is good.As shown in Fig. 4 (d), LMCN20 particle surfaces
Primary particle blurring, as shown in Fig. 4 (e), then spherical morphology is completely damaged for LMCN40 particles.To two kinds of LMNC and LMNC10
Material carries out surface linear scanning EDX power spectrums test, as shown in Fig. 5 (b), it can be seen that obtained without AMMONIA TREATMENT presoma
To corresponding LMNC stratiforms lithium-rich anode material, the content and theoretical calculation (Mn of Mn, Ni and Co:Ni:Co=3:1:1), and
The obtained corresponding LMNC10 stratiforms lithium-rich anode materials of 10min are handled to presoma using ammonium hydroxide, as shown in Fig. 5 (a),
The Ni contents of particle surface be significantly lower than Co contents, i.e., carbonate precursor particle surface Mn, the Ni changed after AMMONIA TREATMENT and
Co constituent contents keep identical metallic element after high temperature lithiation in obtained stratiform lithium-rich anode material
Distribution.
By XRD analysis, as shown in fig. 6, all samples are typical stratiform α-NaFeO2Structure, space group R3m, together
When occur obvious Li between 20 ° -25 °2MnO3Superlattices diffraction maximum is the characteristic peak of stratiform lithium-rich anode material, empty
Between group be C2/m.However, finding out from enlarged drawing, corresponding stratiform lithium-rich anode material is obtained by AMMONIA TREATMENT presoma
In, find the XRD diffraction maximums of Spinel (space group Fd-3m), and as the AMMONIA TREATMENT time is longer, Spinel
Diffraction maximum is more apparent.
As shown in fig. 7, being obtained by TME tests, as shown in Fig. 7 (a), the stratiform richness lithium of AMMONIA TREATMENT presoma is not used
Positive electrode LMNC, crystal structure is pure layer structure, and uses obtained stratiform after AMMONIA TREATMENT presoma 10min
Lithium-rich anode material LMNC10, as shown in Fig. 7 (b), particle surface is there are one layer of apparent Spinel, and Spinel
It is mixed structure between main body layer structure, sees Fig. 7 (c), illustrates that AMMONIA TREATMENT presoma changes its surface chemistry composition
Afterwards, during lithiumation self-induction surface Spinel formation.
Electro-chemical test shows to find out from the first charge-discharge curve of Fig. 8：The obtained stratiform of AMMONIA TREATMENT presoma is rich
In~2.6V, there are one apparent Spinel discharge platforms in the discharge curve of lithium anode material, and untreated samples are flat without this
Platform.The discharge capacity for the first time of LMNC samples obtained by unused AMMONIA TREATMENT is 288.7mAh/g, and coulombic efficiency is 79.5% for the first time,
And the LMNC10 samples obtained by AMMONIA TREATMENT 10min have highest specific discharge capacity, are 300.0mAh/g, for the first time coulombic efficiency
Up to 89.8%.Finding out from Fig. 9 (a), LMNC10 has optimal cycle life, and it is 85% to recycle 100 capacity retention ratios,
And comparative example LMNC materials only have 65.3% by 100 capacity retention ratios of cycle.In addition, the mean voltage of LMNC10 is with following
Ring is failed the most slowly (Fig. 9 (b)), and Fig. 9 (c) and (d) are also further demonstrated that, relative to pure layer structure LMNC,
Since surface introduces Spinel in LMNC10, discharge platform voltage decay is slowed down.Find out from the high rate performance figure of Figure 10,
The high rate performance that LMNC10 has had still has 156.2mAh/g under 10C multiplying powers, and LMNC only has under 10C multiplying powers
111.3mAh/g.The above electrochemical property test explanation after ammonium hydroxide is to the carbonate precursor processing suitable time, then is led to
The chemical property of stratiform lithium-rich anode material can be significantly improved by crossing high temperature lithiumation process self-induction and forming special surface.
Embodiment 2
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ammonium sulfate for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
20min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, is handled
Carbonate precursor afterwards.
(2) carbonate precursor of the ammonium sulfate 20min obtained in untreated and step (1) is burnt at 500 DEG C
6h obtains oxide.
(3) oxide for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio is uniformly mixed, and is set
12h is calcined at 750 DEG C in Muffle furnace, obtains lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ammonium sulfate processing
It is 293.0mAh/g, first charge-discharge efficiency 88.2% to enclose interior first discharge specific capacity；At 0.5C after 100 cycles
Capacity retention ratio is 90.5%；Under the big multiplying powers of 10C, reversible capacity remains as 146.3m Ah/g, shows than unused ammonium sulfate
Handle stratiform lithium-rich anode material (comparative example) more excellent chemical property obtained by presoma.
Embodiment 3
(1) the spherical Mn obtained by Co deposited synthesis is weighed0.75Ni0.25CO3Carbonate precursor 3.0g, is placed in
In 50mL beakers, the sal volatile for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, mechanical agitation
30min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, obtains ammonium hydroxide
The carbonate precursor of processing.
(2) sal volatile obtained in untreated and step (1) is handled into the carbonate precursor of 30min at 400 DEG C
Lower burning 8h, obtains oxide precursor.
(3) oxide precursor for obtaining above-mentioned steps and lithium hydroxide are with [Li]:[M]=1.55:1 ratio mixing
Uniformly, it is placed in Muffle furnace and is calcined for 24 hours at 700 DEG C, obtain lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ammonium carbonate processing
It is 298.0mAh/g (untreated samples 280.0mAh/g), first charge-discharge efficiency 90.3% to enclose interior first discharge specific capacity
(untreated samples 78.6%)；Capacity retention ratio is that 91.4% (untreated samples are after 100 cycles at 0.5C
78.5%)；Under the big multiplying powers of 10C, reversible capacity remains as 158.6m Ah/g (untreated samples are 102.3m Ah/g), shows
Show chemical property more more excellent than lithium-rich anode material obtained by unused ammonium carbonate processing presoma.
Embodiment 4
(1) the spherical Mn obtained by Co deposited synthesis is weighed0.50Ni0.25Co0.25CO3Carbonate precursor 2.0g, sets
In 100mL beakers, the ammonium bicarbonate soln for measuring 50mL2.0mol/L pours into the beaker equipped with carbonate precursor, machinery
10min is stirred, then with distilled water repeatedly wash, filter, dry 12h is finally placed in air dry oven at 100 DEG C, obtains
Treated carbonate precursor.
(2) ammonium bicarbonate soln obtained in untreated and step (1) is handled into the carbonate precursor of 30min 600
4h is burnt at DEG C, obtains oxide precursor.
(3) oxide precursor for obtaining above-mentioned steps and lithium nitrate are with [Li]:[M]=1.1:1 ratio mixing is equal
It is even, it is placed in Muffle furnace and calcines 8h at 900 DEG C, obtain lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage after electro-chemical test shows ammonium hydrogen carbonate processing
First discharge specific capacity is 260.0mAh/g (untreated samples 232.0mAh/g) in range, and first charge-discharge efficiency is
88.0% (untreated samples 79.3%)；Capacity retention ratio is 88.5% (untreated sample after 100 cycles at 0.5C
75.2%) product are；Under the big multiplying powers of 10C, reversible capacity remains as 140.6m Ah/g, and (untreated samples are 86.2m Ah/
G), display chemical property more more excellent than lithium-rich anode material obtained by unused ammonium hydrogen carbonate processing presoma.
Embodiment 5
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ammonium chloride solution for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
30min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, is handled
Carbonate precursor afterwards.
(2) carbonate precursor of the ammonium chloride solution 20min obtained in untreated and step (1) is burnt at 500 DEG C
6h obtains oxide.
(3) oxide for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio is uniformly mixed, and is set
12h is calcined at 750 DEG C in Muffle furnace, obtains lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ammonium chloride processing
It is 286.0mAh/g, first charge-discharge efficiency 85.0% to enclose interior first discharge specific capacity；At 0.5C after 100 cycles
Capacity retention ratio is 89.2%；Under the big multiplying powers of 10C, reversible capacity remains as 134.5m Ah/g, shows than unused ammonium chloride
Handle stratiform lithium-rich anode material (comparative example) more excellent chemical property obtained by presoma.
Embodiment 6
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ammonium nitrate solution for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
20min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, is handled
Carbonate precursor afterwards.
(2) carbonate precursor of the ammonium nitrate solution 20min obtained in untreated and step (1) is burnt at 500 DEG C
6h obtains oxide.
(3) oxide for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio is uniformly mixed, and is set
12h is calcined at 750 DEG C in Muffle furnace, obtains lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ammonium nitrate processing
It is 288.4mAh/g, first charge-discharge efficiency 86.0% to enclose interior first discharge specific capacity；At 0.5C after 100 cycles
Capacity retention ratio is 88.2%；Under the big multiplying powers of 10C, reversible capacity remains as 141.3m Ah/g, shows than unused ammonium nitrate
Handle stratiform lithium-rich anode material (comparative example) more excellent chemical property obtained by presoma.
Embodiment 7
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ammonium acetate solution for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
30min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, is handled
Carbonate precursor afterwards.
(2) carbonate precursor of the ammonium acetate solution 30min obtained in untreated and step (1) is burnt at 500 DEG C
6h obtains oxide.
(3) oxide for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio is uniformly mixed, and is set
12h is calcined at 750 DEG C in Muffle furnace, obtains lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ammonium acetate processing
It is 289.4mAh/g, first charge-discharge efficiency 85.5% to enclose interior first discharge specific capacity；At 0.5C after 100 cycles
Capacity retention ratio is 87.6%；Under the big multiplying powers of 10C, reversible capacity remains as 143.6m Ah/g, shows than unused ammonium acetate
Handle stratiform lithium-rich anode material (comparative example) more excellent chemical property obtained by presoma.
Embodiment 8
(1) the spherical Mn synthesized by hydro-thermal method is weighed0.6Ni0.2Co0.2CO3Carbonate precursor 2.0g, is placed in
In 50mL beakers, the ethylenediamine solution for measuring 30mL2.0mol/L pours into the beaker equipped with carbonate precursor, magnetic agitation
40min, then repeatedly washing, filtering are carried out with distilled water, it is finally placed in air dry oven at 80 DEG C dry 12h, is handled
Carbonate precursor afterwards.
(2) it will obtain handling the carbonate precursor of 40min 500 through ethylenediamine solution in untreated and step (1)
6h is burnt at DEG C, obtains oxide.
(3) oxide for obtaining above-mentioned steps and lithium carbonate are with [Li]:[M]=1.42:1 ratio is uniformly mixed, and is set
16h is calcined at 750 DEG C in Muffle furnace, obtains lithium-rich anode material.
Obtained lithium-rich anode material is in 0.1C, 2.0-4.6V voltage model after electro-chemical test shows ethylenediamine processing
It is 290.4mAh/g, first charge-discharge efficiency 86.7% to enclose interior first discharge specific capacity；At 0.5C after 100 cycles
Capacity retention ratio is 87.2%；Under the big multiplying powers of 10C, reversible capacity remains as 139.0mAh/g, shows than unused ethylenediamine
Handle stratiform lithium-rich anode material (comparative example) more excellent chemical property obtained by presoma.
Claims (4)
1. the surface texture and chemical composition synchronization modulation method of a kind of stratiform lithium-rich anode material, the stratiform lithium-rich anode
The general formula of material is：xLi2MnO3·(1-x)LiMO2Or Li1+x[M]1-xO2, in formula:M is one or more of Mn, Co, Ni,
0<x<1；The main body of the stratiform lithium-rich anode material particle is layer structure, and surface is Spinel, layer structure and spinelle
It is transition mixed phase between phase, and the chemical composition on surface is different from the chemical composition of main body, includes the following steps：
(1) carbonate precursor is placed in processing agent solution, after uniform stirring processing, is washed with distilled water, filters, dries,
The carbonate precursor that obtains that treated；
It (2) will treated that carbonate precursor calcines 4-8h at 400-600 DEG C obtains oxide；The oxide that will be obtained again
It is uniformly mixed for 1.1~1.55 by the ratio between molal quantity of lithium and transition metal total mole number with Li source compound；It will obtain
Mixture calcine 8-24h at 700-900 DEG C, obtain surface modification lithium-rich anode material.
2. the surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material according to claim 1, step
It is rapid 1) in inorganic agent include in ammonium hydroxide, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium nitrate, ammonium acetate or ethylenediamine
One or more of salt-mixtures.
3. the surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material according to claim 1, step
It is rapid 1) in agitating mode using magnetic agitation or mechanical agitation.
4. the surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material according to claim 1, step
It is rapid 2) described in Li source compound include one or more of lithium carbonate, lithium hydroxide or lithium nitrate mixture.
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