CN110416499A - Lithium-rich anode material and preparation method thereof - Google Patents
Lithium-rich anode material and preparation method thereof Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to field of lithium ion battery, and in particular to lithium-rich anode material and preparation method thereof.Method includes the following steps: (1) reacts transition metal salt solution with the life of coprecipitation reaction solution hybrid concurrency, carbonate precursor is made；(2) carbonate precursor prepared by step (1) is mixed with lithium source, is then successively ground, is calcined；Wherein, the coprecipitation reaction solution is the mixed solution of bicarbonate solution or bicarbonate and carbonate.This method preparation process is simple, is not necessarily to complex device, and reaction duration is shorter, and the rich lithium material prepared has higher capacity, and cycle performance is preferable, can satisfy the market demand.There is secondary ball pattern, tap density 1.4-2.1g/cm using lithium-rich anode material made from this method3, general formula xLi2MO3·(1‑x)LiMO2, wherein at least one of M Ni, Co, Mn, Fe and Cr, 0 < x < 1.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to lithium-rich anode material and preparation method thereof.
Background technique
In recent years, the application field of lithium ion battery has been widened since miniature electric portable device is gradually to EV/
The fields such as HEV/PHEV.But the application on electric car still faces that course continuation mileage is short, and high expensive and safety etc. are asked
Topic, these all seriously constrain its large-scale application and promote.In order to make electric car course continuation mileage be more than 500 kilometers, realize
The large-scale promotion of electric car researches and develops the inexorable trend that high-energy density power lithium-ion battery of new generation is future development.
Lithium-rich positive electrode Li [LixM1-x]O2Or it is written as Li1+xM1-xO2(0 < x < 1), if regarding two kinds of stratiforms as
The solid solution that substance is formed, can be expressed as (1-x) Li2NO3·xLiMO2(0 < x < 1), wherein N=Mn/Ti etc., M=Ni/Co/
The combination of one or more of Mn/Cr etc..Lithium-rich positive electrode theoretical specific capacity is more than 300mAh/g, and operating voltage is big
In 4.5V, becomes the important research object of lithium ion battery with high energy density positive electrode, cause people to such material
Extensive concern.
Two or more transition metal ions is usually contained in lithium-rich positive electrode, in order to guarantee transition metal
Uniform ion distribution, obtains the phase pure material of expected component, and the selection of preparation method is extremely important.Currently, lithium-rich anode material
Main preparation methods be coprecipitation, and different transition metal ions solubility product constants have larger difference in material, therefore,
Want to reach different metal ions co-precipitation, the control of the techniques such as reaction pH, temperature, complexing agent, reaction rate, protection gas is very
It is important.Common coprecipitation reaction equipment is coprecipitation reaction kettle, is monitored by online pH, continuous feedback reaction system pH, is led to
The stability contorting that control reaction solution feed rate realizes pH is crossed, the device is complicated leads to higher cost, and charging rate for this method
Compared with determining that its reaction time is long slowly, generally higher than 20h.
A kind of preparation method of high capacity spherical shape lithium-rich anode material is disclosed in CN103956479A.By the sulfuric acid of nickel cobalt manganese
The coprecipitation reaction kettle of stirring is added dropwise in salting liquid, sodium carbonate liquor and ammonium hydroxide simultaneously, reacts under the conditions of pH is 7-9, will
The obtained filtering of presoma solidliquid mixture, separation, washing, drying, after carbonate precursor pyrolytic to oxide, then
Lithium-rich anode material is obtained with lithium carbonate mixed sintering.Coprecipitation reaction described in the invention needs coprecipitation reaction kettle, required
It is at high cost that the device is complicated, and pH changes with chemical reaction, keeps reaction pH regulation difficulty larger, because of reaction solution adding speed
Slowly, so it is longer the time required to reaction.
A kind of high-tap density lithium-rich manganese-based anode material and preparation method thereof is disclosed in CN106129360A.By transition
Certain speed is slowly added to reaction vessel respectively for metal salt solution and hydroxide solution, at 30-70 DEG C, the condition of pH=10
Lower co-precipitation prepares presoma, and presoma is filtered, washed, is dried, then obtains lithium-rich anode material with lithium source mixed calcining.It should
Coprecipitation reaction speed described in invention is slower, reacts pH higher and carries out with reacting, the variation of chemical system is difficult to it
It is uncontrollable to easily lead to synthetic material pattern for stability contorting.
Summary of the invention
The purpose of the invention is to overcome to react required time existing for the preparation method of existing lithium-rich anode material
Longer, the problems such as preparation process is complicated, at high cost, provides a kind of lithium-rich anode material and preparation method thereof, preparation method tool
It is short, simple process the time required to having the advantages that reaction, at low cost, and the lithium-rich anode material prepared has improved electrochemistry
Performance.
To achieve the goals above, the present invention provides a kind of preparation method of lithium-rich anode material, this method include with
Lower step:
(1) transition metal salt solution is reacted with the life of coprecipitation reaction solution hybrid concurrency, carbonate precursor is made；
(2) carbonate precursor made from step (1) is mixed with lithium source, is then successively ground, is calcined；
Wherein, the coprecipitation reaction solution is the mixed solution of bicarbonate solution or bicarbonate and carbonate.
The present invention also provides the lithium-rich anode materials prepared by the above method.
Through the above technical solutions, the attainable technical effect of present invention institute is as follows:
1) during preparing carbonate precursor, bicarbonate radical, which can hydrolyze, generates CO2, maintain system oxygen debt
Environment protects transition metal ions without being individually added into nitrogen, it is therefore prevented that transition metal ions is oxidized, to guarantee
Reaction is gone on smoothly, and can obtain desired reaction product；
2) during preparing carbonate precursor, use ammonium hydrogen carbonate as coprecipitation reaction solution, ammonium hydrogen carbonate
Hydrolysis ammonium ion, is equivalent to complexing agent, promotes the different transition metal ions co-precipitations in the present invention；
3) lithium-rich anode material of method preparation of the present invention is detected as R-3m layer structure through XRD, and in 20-
It is observed that Li between 25 °2MnO3Characteristic peak illustrate that material is typical rich lithium structure furthermore without other miscellaneous peaks；
4) lithium-rich anode material of method preparation of the present invention has fine and close secondary ball pattern, vibration with higher
Real density；
5) lithium-rich anode material discharge capacity with higher (first charge-discharge capacity up to 247.7mAh/g,
0.1C discharge capacity is up to 257.6mAh/g), cycle performance is preferable, can satisfy the market demand；
6) the preparation method simple process of lithium-rich anode material of the present invention, without complex device (such as simple
Can be realized in container), reaction duration is shorter (to be less than 1h the time required to entire reaction, prepares rich lithium with common coprecipitation
The time of positive electrode is compared greater than 20h, shortens the reaction time).
Detailed description of the invention
Fig. 1 is the preparation flow signal of carbonate precursor in the preparation method of lithium-rich anode material of the present invention
Figure；
Fig. 2 is the SEM figure of lithium-rich anode material prepared by embodiment 1；
Fig. 3 is the X-ray diffractogram of lithium-rich anode material prepared by embodiment 1；
Fig. 4 is the first charge-discharge curve of lithium-rich anode material prepared by embodiment 1；
Fig. 5 is the cycle performance of lithium-rich anode material prepared by embodiment 1.
Description of symbols
1 transition metal salt solution；2 coprecipitation reaction solution；3 carbonate precursors
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of lithium-rich anode material of the present invention the following steps are included:
(1) transition metal salt solution is reacted with the life of coprecipitation reaction solution hybrid concurrency, carbonate precursor, tool is made
Body is as shown in Figure 1；
(2) carbonate precursor prepared by step (1) is mixed with lithium source, is then successively ground, is calcined.
In step (1), the transition metal salt can be the conventional selection of this field.In the preferred case, the mistake
Crossing transition metal in metal salt is at least one of nickel, cobalt, manganese, iron and chromium, the transition metal salt can for nickel, cobalt,
At least one of soluble-salt of these transition metal such as manganese, iron, chromium, such as sulfate, nitrate, oxalates, acetate.
In step (1), the coprecipitation reaction solution is the mixed of bicarbonate solution or bicarbonate and carbonate
Close solution.
In the present invention, the bicarbonate can be various conventional water soluble carbonate hydrogen salts.In the preferred case, institute
Stating bicarbonate is ammonium hydrogen carbonate and/or sodium bicarbonate, most preferably ammonium hydrogen carbonate.Bicarbonate radical can hydrolyze in reaction process
Generate CO2, so that system is maintained oxygen debt environment, transition metal ions protected without being individually added into nitrogen, it is therefore prevented that mistake
It crosses metal ion to be oxidized, to ensure that reaction is gone on smoothly, desired reaction product can be obtained.
In the present invention, the carbonate can be various conventional water soluble carbonates.In the preferred case, the carbon
Hydrochlorate is at least one of lithium carbonate, sodium carbonate and potassium carbonate.
In a particular embodiment, the coprecipitation reaction solution is ammonium bicarbonate soln, due to different transition metal
Ion solubility product constant has larger difference, needs the effect of complexing agent to can be only achieved different metal ions co-precipitation, in this hair
In bright, when the bicarbonate is ammonium hydrogen carbonate, the ammonium ion of ammonium hydrogen carbonate hydrolysis carries out network to reacting metal ion
It closes, the ammonium ion of ammonium hydrogen carbonate hydrolysis is equivalent to complexing agent at this time, (can be with the transition metal ions in the present invention
Nickel, cobalt, manganese, iron, chromium etc.) it is complexed, making the different transition metal ions in the present invention (can be nickel, cobalt, manganese, iron, chromium
Deng) achieve the purpose that co-precipitation, so that reaction process is simpler；In addition, in the present invention, when the bicarbonate is carbonic acid
Bicarbonate radical, which can hydrolyze, when hydrogen ammonium, in reaction process generates CO2, so that system is maintained oxygen debt environment, without being individually added into nitrogen
Gas protects transition metal ions, it is therefore prevented that and transition metal ions is oxidized, thus ensure that reaction is gone on smoothly, it can
Obtain desired reaction product.
In the present invention, the total concentration of salt can be 1~3mol/L in the coprecipitation reaction solution, specifically, such as
Can for 1mol/L, 1.2mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, 2.2mol/L,
It is any in the range that any two in 2.4mol/L, 2.6mol/L, 2.8mol/L, 3mol/L and these point values are constituted
Value.Salt refers to bicarbonate therein perhaps carbonate or bicarbonate and carbonate in the coprecipitation reaction solution
Combination.
In the present invention, the concentration of the transition metal salt can be 1-2.2mol/L, specifically, such as can be
Appointing in 1mol/L, 1.2mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.8mol/L, 2mol/L and these point values
Arbitrary value in two ranges constituted of anticipating.
The transition metal in salt and the transition metal salt solution in step (1), in the coprecipitation reaction solution
The molar ratio of salt can be 1~2:1, preferably 1.2~1.8:1.Specifically, for example, can for 1,1.2,1.4,1.6,1.8,
2.0 and these point values in the range that is constituted of any two in arbitrary value.It is rubbed by the material amounts both adjusted
Your ratio, can control with simple realization to system pH.
In step (1), the condition of the reaction may include: that temperature is 10-80 DEG C, and the time is 10-60 minutes, pH value
It is 7.2~9.5；Preferably temperature is 20-50 DEG C, and the time is 20-40 minutes, pH value 7.5-9；Further preferably temperature is
40 DEG C, the time is 30 minutes, pH value 8.5.Specifically, such as temperature can be 10 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40
DEG C, 45 DEG C, 50 DEG C, in the range that is constituted of any two in 60 DEG C 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C and these point values
Arbitrary value；Time can be 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 points
The arbitrary value in range that any two in clock, 55 minutes, 60 minutes and these point values are constituted；PH value can for 7.2,
7.5,8,8.5,9,9.5 and these point values in the range that is constituted of any two in arbitrary value.Of the present invention
In method, suitable temperature, reaction time and pH value ensure that reaction sufficiently carries out, and the performance for obtaining product is more excellent.
In the present invention, the reaction carries out under stiring, and stirring rate can be 10-1000rpm, preferably 200-
400rpm.Specifically, for example, can for 10rpm, 50rpm, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm,
400rpm、450rpm、500rpm、550rpm、600rpm、650rpm、700rpm、750rpm、800rpm、850rpm、900rpm、
The arbitrary value in range that any two in 950rpm, 1000rpm and these point values are constituted.However, the present invention can also
To carry out without stirring, but due to reaction and it is uneven, so the pattern of obtained lithium-rich anode material and
Properties of product are bad, i.e., ensure that abundant reaction by stirring, obtained carbonate precursor performance is preferable.
The stirring can for it is any it is conceivable that conventional agitating mode, preferably mechanical stirring or magnetic force stir
It mixes, most preferably magnetic agitation.Specifically, mechanical stirring can use arm stirrer, propeller type mixer, turbine type
The blenders such as blender, helix(ribbon type) agitator, anchor formula and gate stirrer are stirred.Specified otherwise is not made in the present invention
In the case where, the agitating mode used in the present embodiment is magnetic agitation.
In the present invention, in order to which dry carbonate precursor is made, step (1) further includes carrying out to reaction mixture
Filter, washing and drying.Heretofore described is filtered, washed and dried as any routine operation being contemplated that, the filtering
With no restrictions, described wash uses instrument, cleaning solvent, mode of washing and washing for mode, filtering instrument and filtering times etc.
Number etc. with no restrictions, cleaning solvent can for deionized water, dehydrated alcohol etc. are any can be with conceivable solvent, the drying
Used instrument, drying mode, drying time etc. are with no restrictions.Described be filtered, washed and dried can be under normal temperature and pressure
It carries out, or carried out under high temperature and pressure, it is therefore preferable to which vacuum high-temperature is dry, and the high temperature is preferably 100-200 DEG C, most
It is preferred that 120-180 DEG C, it specifically, such as can be 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170
DEG C, 180 DEG C, 190 DEG C, the arbitrary value in the range that is constituted of any two in 200 DEG C and these point values.When described dry
Between can be 1-20h, specifically, such as can be any two institute structure in 1h, 5h, 10h, 15h, 20h and these point values
At range in arbitrary value.In a specific embodiment, the present invention is to wash after filtering reaction product, then at 120 DEG C
It is dried in vacuo 10h.
In step (2), the lithium source can be the conventional selection of this field.In the preferred case, the lithium source can be with
For the various conventional soluble salt of lithium, such as at least one of lithium nitrate, lithium acetate, lithium oxalate, lithium hydroxide and lithium carbonate.In
In specific embodiment, the lithium source of the present invention can be lithium hydroxide.
In step (2), the lithium source is made with stoichiometric excess than 3~5wt% relative to the carbonate precursor
With.For example, the lithium source relative to the carbonate precursor can be stoichiometric excess ratio be 3wt%, 3.5wt%,
The arbitrary value in range that any two in 4wt%, 4.5wt%, 5wt% and these point values are constituted.Specific real
It applies in mode, the lithium source is relative to the carbonate precursor with stoichiometric excess ratio 3wt% use.
In step (2), the calcination process is the conventional selection of this field.Preferably, the process of the calcining includes:
The 400-600 DEG C of heat preservation 3-10h in the air of circulation, later in 800-1000 DEG C of heat preservation 5-10h；More preferably in the sky of circulation
500 DEG C of heat preservation 5h in gas, later in 800-900 DEG C of heat preservation 5-10h.Specifically, can in the air of circulation 400 DEG C,
The arbitrary value in range that any two in 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C and these point values are constituted, heat preservation 3h,
The arbitrary value in range that any two in 4h, 5h, 6h, 7h, 8h, 9h, 10h and these point values are constituted, later 800
DEG C, 850 DEG C, 900 DEG C, 950 DEG C, the arbitrary value in the range that is constituted of any two in 1000 DEG C and these point values, protect
The arbitrary value in range that any two in warm 5h, 6h, 7h, 8h, 9h, 10h and these point values are constituted.
The lithium-rich anode material being prepared by the process described above, general formula xLi2MO3·(1-x)LiMO2,
In, at least one of M Ni, Co, Mn, Fe and Cr, 0 < x < 1.Preferably, the lithium-rich anode material is scanned through SEM, can be with
It is found to have the secondary spherical pattern of morphological rules；The lithium-rich anode material is detected as R-3m layer structure through XRD, and
It is observed that Li between 20-25 °2MnO3Characteristic peak illustrate that material is typical rich lithium structure furthermore without other miscellaneous peaks；The richness
Lithium anode material is tested through tap density meter, tap density with higher, tap density 1.4-2.1g/cm3, it is preferable that
Tap density is 1.7-2.1g/cm3, such as can be 1.4g/cm3、1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3、
1.9g/cm3、2.0g/cm3、2.1g/cm3And the arbitrary value in the range that is constituted of any two in these point values；It is described
Lithium-rich anode material discharge capacity with higher, it is preferable that under 0.1C for the first time discharge capacity up to 202.5-257.6mAh/g,
Specifically, such as 202.5mAh/g, 206.1mAh/g, 223.8mAh/g, 232.4mAh/g, 247.7mAh/g, 257.6mAh/g
And the arbitrary value in the range that is constituted of any two in these point values；The lithium-rich anode material has preferably simultaneously
Cycle performance, it is preferable that lithium-rich anode material capacity retention ratio about 83.3% behind circulation 100 weeks under 0.2C, it can
Meet the market demand.Heretofore described SEM is scanned, XRD detection, tap density meter is tested, discharge capacity is tested and followed
Ring performance test is the routine operation of this field.
Embodiment 1
It the acetate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Ammonium hydrogen carbonate and sodium carbonate are dissolved in deionized water with molar ratio 1:3 and are configured to 100mL by the transition metal salt solution of 1.5mol/L
Concentration is the reaction A liquid of 3mol/L, prepared transition metal salt solution is directly mixed with A liquid is reacted, under the conditions of 40 DEG C
With the stirring of 400rpm rate, reaction is produced after having bubble generation, reaction pH to maintain after 30s in reaction process 9.5,30 minutes
Object obtains lithium-rich anode material carbonate precursor N through suction filtration, washing, 120 DEG C of vacuum drying 10hi0.2Co0.2Mn0.46CO3。
Amount addition by the carbonate precursor and lithium hydroxide after drying with stoichiometric excess than 3 weight %, sufficiently
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 10h in the air of circulation after grinding
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material.
The lithium-rich anode material being prepared according to embodiment 1 SEM detection is done into, as shown in Fig. 2, can from Fig. 2
Out, what is be prepared has preferable spherical morphology；
The lithium-rich anode material being prepared according to embodiment 1 XRD detection is done into, as shown in figure 3, through standard PDF card
Piece compares, it is possible to find material is typical layer structure, and at 20~25 ° it is observed that apparent Li2MnO3Characteristic peak, XRD spread out
It is stronger to penetrate peak, illustrates that material has preferable crystallinity；
First charge-discharge curve under 0.1C is depicted simultaneously, as shown in figure 4,1 indicates charging, 2 indicate electric discharge, can from figure
To find out, there is apparent platform in 4.5V or so in discharge capacity 247.7mAh/g, charging curve, fills for typical rich lithium
Electric curve；
Fig. 5 is the cycle performance of the lithium-rich anode material that is prepared according to embodiment 1 at 0.2C, can be with from Fig. 5
To find out, the preceding 18 weeks capacity attenuations of circulation are obvious, it tends towards stability later, capacity retention ratio about 83.3% after circulation 100 weeks.
Embodiment 2
The acetate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 23:23:53 and is configured to 100mL concentration as 2mol/L
Transition metal salt solution, sodium bicarbonate and sodium carbonate with molar ratio 1:3 are dissolved in deionized water are configured to 100mL concentration and be
The reaction A liquid of 3mol/L directly mixes prepared transition metal salt solution with A liquid is reacted, under the conditions of 25 DEG C with
200rpm rate stirs, by reaction product after having bubble generation, reaction pH to maintain after 30s in reaction process 8.5,30 minutes
Rich lithium material carbonate precursor Ni is obtained through suction filtration, washing, 120 DEG C of vacuum drying 10h0.2Co0.2Mn0.46CO3。
By after drying carbonate precursor and lithium hydroxide added with the amount of stoichiometric excess ratio 3wt%, sufficiently grind
500 DEG C heat preservation 5 hours finally obtain to obtain later in 900 DEG C of high temperature holding 5h in the air of circulation after mill
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 232.4mAh/g.
Embodiment 3
It the sulfate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Sodium bicarbonate and sodium carbonate are dissolved in deionized water with molar ratio 1:3 and are configured to 100mL by the transition metal salt solution of 1.5mol/L
Concentration is the reaction A liquid of 1.5mol/L, prepared transition metal salt solution is mixed with reacting in the direct beaker of A liquid, 50
It is stirred under the conditions of DEG C with 1000rpm rate, there is bubble generation in reaction process, reaction pH is maintained 7.8,60 minutes after 30s
Reaction product is obtained into lithium-rich anode material carbonate precursor through suction filtration, washing, 120 DEG C of vacuum drying 10h afterwards
Ni0.2Co0.2Mn0.46CO3。
Amount addition by the carbonate precursor and lithium nitrate after drying with stoichiometric excess than 5 weight %, sufficiently grinds
600 DEG C heat preservation 3 hours finally obtain later in 1000 DEG C of high temperature holding 5h in the air of circulation after mill
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 221.6mAh/g.
Embodiment 4
The acetate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 23:23:53 and is configured to 100mL concentration as 2mol/L
Transition metal salt solution, ammonium hydrogen carbonate and lithium carbonate with molar ratio 1:4 are dissolved in deionized water are configured to 100mL concentration and be
The reaction A liquid of 3mol/L directly mixes prepared transition metal salt solution with A liquid is reacted, at 20 °C with
400rpm rate stirs, by reaction product after having bubble generation, reaction pH to maintain after 30s in reaction process 8.5,30 minutes
Lithium-rich anode material carbonate precursor Ni is obtained through suction filtration, washing, 120 DEG C of vacuum drying 10h0.2Co0.2Mn0.46CO3。
By after drying carbonate precursor and lithium hydroxide added with the amount of stoichiometric excess ratio 3wt%, sufficiently grind
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 5h in the air of circulation after mill
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 223.8mAh/g.
Embodiment 5
It the oxalates of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Ammonium hydrogen carbonate and lithium carbonate are dissolved in deionized water with molar ratio 1:4 and are configured to 100mL by the transition metal salt solution of 1.0mol/L
Concentration is the reaction A liquid of 1.8mol/L, prepared transition metal salt solution is directly mixed with A liquid is reacted, in 45 DEG C of conditions
Under with the stirring of 400rpm rate, have bubble generation in reaction process, reaction pH maintains 8.3 after 30s, after forty minutes will reaction
Product obtains lithium-rich anode material carbonate precursor Ni through suction filtration, washing, 120 DEG C of vacuum drying 10h0.2Co0.2Mn0.46CO3。
Amount addition by the carbonate precursor and lithium oxalate after drying with stoichiometric excess than 3 weight %, sufficiently grinds
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 5h in the air of circulation after mill
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 213.4mAh/g.
Embodiment 6
It the acetate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Sodium bicarbonate and potassium carbonate are dissolved in deionized water with molar ratio 1:3 and are configured to 100mL by the transition metal salt solution of 1.0mol/L
Concentration is the reaction A liquid of 1.2mol/L, prepared transition metal salt solution is directly mixed with A liquid is reacted, the co-precipitation
The total concentration of salt is 1.3mol/L in reaction solution, and with the stirring of 400rpm rate under the conditions of 25 DEG C, reaction pH is maintained after 30s
Reaction product is obtained into lithium-rich anode material carbonic acid salt precursor through suction filtration, washing, 120 DEG C of vacuum drying 10h after 8,30 minutes
Body Ni0.2Co0.2Mn0.46CO3。
Amount addition by the carbonate precursor and carbonic acid after drying with stoichiometric excess than 3 weight %, is fully ground
500 DEG C heat preservation 5 hours in the air of circulation afterwards, keep 5h in 900 DEG C of high temperature later, finally obtain
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 216.7mAh/g.
Embodiment 7
The acetate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 14:21:65 and is configured to 100mL concentration as 2mol/L
Transition metal salt solution, by sodium bicarbonate be dissolved in deionized water be configured to 100mL concentration be 3mol/L reaction A liquid, will match
The transition metal salt solution made is directly mixed with A liquid is reacted, and is stirred under the conditions of 80 DEG C with 200rpm rate, in reaction process
By reaction product through suction filtration, washing, 120 DEG C of vacuum drying after thering is bubble generation, reaction pH to maintain after 30s 8.7,30 minutes
10h obtains rich lithium material carbonate precursor Ni0.14Co0.21Mn0.65CO3。
By after drying carbonate precursor and lithium hydroxide added with the amount of stoichiometric excess ratio 3wt%, sufficiently grind
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 5h in the air of circulation after mill
Li1.13Ni0.12Co0.18Mn0.56O2Lithium-rich anode material, 0.1C discharge capacity about 202.5mAh/g.
Embodiment 8
The acetate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 14:21:65 and is configured to 200mL concentration as 1mol/L
Transition metal salt solution, by sodium bicarbonate be dissolved in deionized water be configured to 100mL concentration be 2mol/L reaction A liquid, will match
The transition metal salt solution made is mixed with reacting in the direct beaker of A liquid, at 20 °C with the stirring of 10rpm rate, reaction
There is bubble generation in the process, reaction pH maintains 8.8 after 30s, after ten minutes, by reaction product through suction filtration, washing, 120 DEG C
Vacuum drying 10h obtains lithium-rich anode material carbonate precursor Ni0.14Co0.21Mn0.65CO3。
Amount addition by the carbonate precursor and lithium hydroxide after drying with stoichiometric excess than 3 weight %, sufficiently
400 DEG C heat preservation 10 hours finally obtain later in 800 DEG C of high temperature holding 10h in the air of circulation after grinding
Li1.13Ni0.12Co0.18Mn0.56O2Lithium-rich anode material, 0.1C discharge capacity about 204.3mAh/g.
Embodiment 9
The acetate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 14:21:65 and is configured to 100mL concentration as 2mol/L
Transition metal salt solution, by ammonium hydrogen carbonate be dissolved in deionized water be configured to 100mL concentration be 2mol/L reaction A liquid, will match
The transition metal salt solution made with react A liquid and directly mixed in beaker, with the stirring of 200rpm rate under the conditions of 10 DEG C, instead
Should during there are a large amount of bubbles to generate, reaction pH maintained after 30s 7.2,30 minutes after by reaction product through suction filtration, washing,
120 DEG C of vacuum drying 10h obtain rich lithium material carbonate precursor Ni0.14Co0.21Mn0.65CO3。
By after drying carbonate precursor and lithium hydroxide added with the amount of stoichiometric excess ratio 3wt%, sufficiently grind
500 DEG C heat preservation 5 hours finally obtain later in 800 DEG C of high temperature holding 10h in the air of circulation after mill
Li1.13Ni0.12Co0.18Mn0.56O2Lithium-rich anode material, 0.1C discharge capacity about 206.1mAh/g.
Embodiment 10
The nitrate of nickel, cobalt, manganese is dissolved in deionized water with molar ratio 14:21:65 and is configured to 100mL concentration as 2mol/L
Transition metal salt solution, by ammonium hydrogen carbonate be dissolved in deionized water be configured to 200mL concentration be 1mol/L reaction A liquid, will match
The transition metal salt solution made with react A liquid and directly mixed in beaker, with the stirring of 200rpm rate under the conditions of 25 DEG C, instead
There should be in the process a large amount of bubbles to generate, reaction pH maintains 8 after 30s, after twenty minutes by reaction product through suction filtration, washing, 120
DEG C vacuum drying 10h obtain lithium-rich anode material carbonate precursor Ni0.14Co0.21Mn0.65CO3。
Amount addition by the carbonate precursor and lithium acetate after drying with stoichiometric excess than 3 weight %, sufficiently grinds
500 DEG C heat preservation 5 hours finally obtain later in 800 DEG C of high temperature holding 10h in the air of circulation after mill
Li1.13Ni0.12Co0.18Mn0.56O2Lithium-rich anode material, 0.1C discharge capacity about 204.8mAh/g.
Comparative example 1
It the acetate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
The transition metal salt solution of 1.5mol/L, it is 3mol/L's that ammonium hydroxide and sodium carbonate, which are dissolved in deionized water to be configured to 100mL concentration,
A liquid is reacted, prepared transition metal salt solution is directly mixed with A liquid is reacted, is stirred under the conditions of 40 DEG C with 400rpm rate
Mix, there is bubble generation in reaction process, reaction pH maintained after 30s 9.5,30 minutes after by reaction product through suction filtration, washing,
120 DEG C of vacuum drying 10h obtain lithium-rich anode material carbonate precursor Ni0.2Co0.2Mn0.46CO3。
Amount addition by the carbonate precursor and lithium hydroxide after drying with stoichiometric excess than 3 weight %, sufficiently
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 10h in the air of circulation after grinding
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 160.1mAh/g.
Comparative example 2
It the acetate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Sodium hydroxide is dissolved in deionized water and is configured to the reaction A that 100mL concentration is 3mol/L by the transition metal salt solution of 1.5mol/L
Liquid directly mixes prepared transition metal salt solution with A liquid is reacted, with the stirring of 400rpm rate under the conditions of 40 DEG C, instead
By reaction product through suction filtration, washing, 120 DEG C after should thering is bubble generation, reaction pH to maintain after 30s in the process 9.5,30 minutes
Vacuum drying 10h obtains lithium-rich anode material hydroxide precursor Ni0.2Co0.2Mn0.46(OH)2。
By after drying lithium-rich anode material hydroxide precursor and lithium hydroxide with stoichiometric excess than 3 weight %
Amount addition, after being fully ground in the air of circulation 500 DEG C keep the temperature 5 hours, keep 10h in 900 DEG C of high temperature later, it is final
To Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 145.8mAh/g.
Comparative example 3
It the acetate of nickel, cobalt, manganese with molar ratio 23:23:53 is dissolved in deionized water is configured to 100mL concentration and be
Sodium bioxalate is dissolved in deionized water and is configured to the reaction A that 100mL concentration is 3mol/L by the transition metal salt solution of 1.5mol/L
Liquid directly mixes prepared transition metal salt solution with A liquid is reacted, with the stirring of 400rpm rate under the conditions of 40 DEG C, instead
Reaction product is obtained into lithium-rich anode through suction filtration, washing, 120 DEG C of vacuum drying 10h after answering pH to maintain after 30s 6,30 minutes
Material oxalate precursor Ni0.2Co0.2Mn0.46C2O4。
Amount addition by the carbonate precursor and lithium hydroxide after drying with stoichiometric excess than 3 weight %, sufficiently
500 DEG C heat preservation 5 hours finally obtain later in 900 DEG C of high temperature holding 10h in the air of circulation after grinding
Li1.13Ni0.2Co0.2Mn0.46O2Lithium-rich anode material, 0.1C discharge capacity about 115.2mAh/g.
Test case
The lithium-rich anode material that embodiment 1-8 and comparative example 1-3 are obtained is measured in 0.1C discharge capacity, as a result
As shown in table 1.
Table 1
It can be seen that by the result of table 1 and adopt the lithium-rich anode material being obtained by the present invention and have at 0.1C
Higher discharge capacity, and the reaction time is shorter.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of preparation method of lithium-rich anode material, which is characterized in that method includes the following steps:
(1) transition metal salt solution is reacted with the life of coprecipitation reaction solution hybrid concurrency, carbonate precursor is made；
(2) carbonate precursor prepared by step (1) is mixed with lithium source, is then successively ground, is calcined；
Wherein, the coprecipitation reaction solution is the mixed solution of bicarbonate solution or bicarbonate and carbonate.
2. the method according to claim 1, wherein the condition of the reaction includes: temperature in step (1)
It is 10-80 DEG C, preferably 20-50 DEG C, the time is 10-60 minutes, and pH value is 7.2~9.5.
3. method according to claim 1 or 2, which is characterized in that in step (1), the reaction carries out under stiring,
Stirring rate is 10-1000rpm.
4. the method according to claim 1, wherein step (1) is also in order to which dry carbonate precursor is made
Including being filtered, washing and drying to reaction mixture.
5. the method according to claim 1, wherein the salt in step (1), in the coprecipitation reaction solution
Molar ratio with the transition metal salt in transition metal salt solution is 1~2:1, and the concentration of the transition metal salt solution is 1.0-
2.2mol/L。
6. the method according to claim 1, wherein transition metal in the transition metal salt be nickel, cobalt,
At least one of manganese, iron and chromium, the transition metal salt are sulfate, nitrate, oxalates and the second of these transition metal
At least one of hydrochlorate.
7. the method according to claim 1, wherein in the coprecipitation reaction solution, the bicarbonate
For ammonium hydrogen carbonate and/or sodium bicarbonate, the carbonate is at least one of lithium carbonate, sodium carbonate and potassium carbonate, described total
The total concentration of salt is 1~3mol/L in precipitation reaction solution.
8. the method according to claim 1, wherein the lithium source is relative to the carbonate precursor with excess
3~5wt% of stoichiometric ratio is used.
9. method according to claim 1 or 8, which is characterized in that the process of the calcining includes: in the air of circulation
In 400-600 DEG C of heat preservation 3-10h, later in 800-1000 DEG C of calcining 5-10h.
10. method according to claim 1 or 8, which is characterized in that the lithium source is selected from lithium nitrate, lithium acetate, oxalic acid
At least one of lithium, lithium hydroxide and lithium carbonate.
11. the lithium-rich anode material that the method as described in any one of claim 1-10 is prepared.
12. lithium-rich anode material according to claim 11, which is characterized in that the lithium-rich anode material has secondary ball
Pattern, tap density 1.4-2.1g/cm3, it is preferable that tap density 1.7-2.1g/cm3, general formula xLi2MO3·(1-
x)LiMO2, wherein at least one of M Ni, Co, Mn, Fe and Cr, 0 < x < 1.
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