CN107104233A - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN107104233A CN107104233A CN201710385320.7A CN201710385320A CN107104233A CN 107104233 A CN107104233 A CN 107104233A CN 201710385320 A CN201710385320 A CN 201710385320A CN 107104233 A CN107104233 A CN 107104233A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of method for preparing anode material of lithium-ion battery, and methods described mixes lithium source substance, manganese source substance, doping metals material and carbon source material, obtains presoma；By obtained presoma sintering, anode material for lithium-ion batteries is obtained.The present invention has directly synthesized porous spherical metal (such as aluminium) adulterated lithium manganate positive electrode by one step solid state sintering, and its specific capacity, high rate performance and cycle performance show excellent, and purity is high, disclosure satisfy that the application request of positive electrode.Compared with other porous spherical manganate cathode material for lithium synthetic methods, this method advantage is protruded, prepared by the as direct solid-phase sintering of one-step method, and processing step is seldom, simple, cost is low, is very suitable for large-scale production.
Description
Technical field
The invention belongs to battery material field, it is related to a kind of cell positive material, more particularly to a kind of lithium ion battery is just
Pole material and its preparation.
Background technology
In recent years, lithium ion battery causes portable rechargeable equipment to there occurs revolutionary change, nowadays lithium-ion electric
Pond just has an immense impact on to automobile industry, i.e., electric automobile is just gradually replacing traditional fossil energy automobile to turn into of future generation main
Body automobile.
It is well known that the development of electric automobile is largely dependent upon the research and development situation of high performance lithium ion battery, especially
It is the research and development of positive electrode.In general, layer structure LiCoO2Positive electrode is although high with energy density
Advantage, but its expensive, poisonous, security is not high, thus be difficult to meet actual operation requirements and enter electric automobile market.With
Compare, spinel structure LiMn2O4Not only there is higher energy density but also extensive, inexpensive, safe with raw material sources
The outstanding advantages such as property is high, environment-friendly and by the extensive concern of electric automobile industry.Therefore, the reality of manganate cathode material for lithium
Using certainly will promote global range in lithium ion battery industry progress and development, to promote environmental-protecting type electric automobile and
The sustainable development of line related industrial economy has highly important positive effect.But, although LiMn2O4It is used as positive pole material
The lithium ion battery of material possesses the advantage of conventional lithium ion battery, but because it has Jahn-Teller effects and surface appearance
It is to restrict it in electric automobile field to make easily to occur disproportionation so as to cause cycle performance especially high temperature cyclic performance not good enough
Key factor.
In order to improve spinelle LiMn2O4The performance such as multiplying power and circulation, people have developed a variety of ways and meanses, such as metal
With nonmetal doping, Surface coating/modification and size and Morphological control etc..These usual methods often can be to certain
One side performance carries out different degrees of improvement, but often due to method is limited in itself, the factor such as cost or technique is hardly resulted in
Scale practical application.It can all make capacity decrease to some degree as being modified element doping and surface, and size and shape
Often complex process is difficult to control to for looks regulation and control, and cost is high, causes it is difficult to large-scale production.
Porous spherical is highly beneficial because of the unique multiplying power and cycle performance to improving positive electrode of its structure, thus
Receive significant attention.But the cost for the synthesizing porous spherical lithium manganate positive electrode reported at present is high, complex process, and real
The porous spherical manganate cathode material for lithium of existing one-step synthesis doping is extremely difficult, and prepare with scale and production can not be carried out at all.
The A of CN 102931393 disclose a kind of preparation method of the manganate cathode material for lithium of porous spherical structure, i.e., by second
Alcohol is as deposit control agent, using NH4HCO3With MnSO4The uniform-spherical manganese carbonate precipitation of a diameter of 0.5-3 μm of mixing generation,
It is scrubbed to obtain pure spheric manganese carbonate powder, and calcining obtains porous spherical Mn in 10-15 hours at 500-800 DEG C2O3Forerunner
Body powder, finally by obtained Mn2O3It is well mixed, is forged higher than above-mentioned with LiOH by hand lapping, ball milling or mechanical lapping
Burning calcining at 700-900 DEG C of temperature can obtain the positive electrode with obvious loose structure.This method technical process is very
Complexity, need to first prepare spherical alumina manganese template, and the manganese carbonate yield of unit volume solution is extremely low, so generation waste liquid is more, cost
Height, and its process is whard to control, it is difficult to be practically applicable to the prepare with scale of low cost.
CN106356524A discloses a kind of preparation method of hollow sphere manganate cathode material for lithium, i.e., using two kinds of solution
It is simply mixed, obtains micron order hollow sphere manganese carbonate using precipitation reaction, then mix hollow sphere manganese carbonate with lithium salts
Roasting obtains pattern rule, size has the hollow sphere LiMn2O4 material of good chemical property and cyclical stability in the lump
Material.Compared with the past similar utilization precipitation reaction prepares manganese carbonate, this method eliminates whipping process, reduces to a certain extent
Energy consumption.But, the manganese carbonate of this method unit volume solution yields poorly, and produces waste liquid excessively, need to first prepare spherical template, and
And spheric manganese carbonate template preparation technology is complicated, is difficult stability contorting.Therefore, it is also difficult to realize prepare with scale and production.
CN105591094A discloses a kind of preparation method of high performance spherical LiMn2O4 system positive electrode, specific steps
It is：(1) first manganese source and the M containing doped chemical compound and lithium source are uniformly mixed using liquid phase method；(2) again using spraying
Seasoning prepares spherical precursor；(3) and then it is sintered, pulverizes and sieves and prepare high performance spherical lithium manganate positive pole material
Material.This method includes multiple process treatment process, it is necessary to use expensive Special Equipment such as atomization drying equipment, complex steps,
Production cycle is long, and cost is high, is also not susceptible to prepare with scale.
In summary, during porous/hollow ball shape manganate cathode material for lithium is prepared, the common ground of institute's application method
It is that must all prepare spherical alumina manganese or spheric manganese carbonate presoma first, and is sintered again just using precursor as template
Final product can be obtained.Therefore, preparation process and technique very complicated, are difficult to control, and cost is high.So development process it is simple,
Cost is low, being easy to implement the direct solid-phase sintering of large-scale production, to prepare porous spherical LiMn2O4 method very necessary and urgent.
In addition, the LiMn2O4 product prepared using the above method is often existed in terms of specific capacity, high rate performance or cycle performance
Situation about attending to one thing and lose sight of another, that is, improve a certain performance but reduce another performance.Step solid-phase sintering of the present invention
Method can overcome disadvantages mentioned above, and technique is simple, is easy to control, reproducible, cost is relatively low, the material good combination property of preparation, ten
Divide and be easy to large-scale production, actual application prospect is wide.
The content of the invention
For technical problem present in prior art, the present invention provides a kind of anode material for lithium-ion batteries and its preparation
Method, the positive electrode specific capacity, high rate performance and cycle performance show excellent, and purity is high, disclosure satisfy that positive pole material
The application request of material, the preparation method technique is simple, is easy to control, reproducible, cost is relatively low, and the material of preparation is comprehensive
Close performance good, be easy to large-scale production, actual application prospect is wide.
To reach above-mentioned purpose, the present invention uses following technical scheme：
One of the object of the invention is to provide a kind of method for preparing anode material of lithium-ion battery, and methods described includes following
Step：
(1) lithium source substance, manganese source substance, doping metals material and carbon source material are mixed, obtains presoma；
(2) presoma for obtaining step (1) is sintered, and obtains anode material for lithium-ion batteries.
As currently preferred technical scheme, the mol ratio of step (1) carbon source material and the lithium source substance is
(5~20):1, such as 5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:
1、19:1 or 20:1 etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range,
Preferably (5~12):1.
Wherein, carbon source material plays a part of pore creating material and template.
As currently preferred technical scheme, step (1) described lithium source substance, manganese source substance and doping metals material
Mol ratio is (1.02~1.08):(2-x):X, such as 1.02:(2-x):x、1.03:(2-x):x、1.04:(2-x):x、1.05:
(2-x):x、1.06:(2-x):x、1.07:(2-x):X or 1.08:(2-x):X etc., it is not limited to cited numerical value, should
Other unrequited numerical value are equally applicable in number range, wherein 0 ＜ x≤0.2.
Wherein, x can be 0.01,0.02,0.05,0.08,0.10,0.12,0.15,0.18 or 0.20 etc., but simultaneously not only
It is limited to other unrequited numerical value in cited numerical value, the number range equally applicable,
As currently preferred technical scheme, the lithium source substance includes lithium carbonate, lithium hydroxide, lithia, oxalic acid
Any one in lithium, lithium acetate or lithium nitrate or at least two combination, the combination is typical but non-limiting examples have：Carbonic acid
The combination of lithium and lithium hydroxide, the combination of lithium hydroxide and lithia, combination, lithium oxalate and the lithium acetate of lithia and lithium oxalate
Combination, the combination of lithium acetate and lithium nitrate, lithium nitrate and the combination of lithium carbonate or lithium carbonate, lithium hydroxide and small sour pears group
Close etc..
Preferably, the manganese source substance includes manganous bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, sulfuric acid
Any one in manganese or manganese acetate or at least two combination, the combination is typical but non-limiting examples have manganous bromide and carbonic acid
The combination of manganese, the combination of manganese carbonate and manganese chloride, the combination of manganese chloride and manganese oxide, the combination of manganese oxide and manganese nitrate, nitric acid
The combination of manganese and manganese oxalate, the combination of manganese oxalate and manganese sulfate, the combination of manganese sulfate and manganese acetate, the group of manganese acetate and manganous bromide
Conjunction or the combination of manganous bromide, manganese carbonate and manganese chloride etc..
As currently preferred technical scheme, step (1) the doping metals material includes silicon source material, copper source material
Or any one in the material of silver-colored source or at least two combination, the combination is typical but non-limiting examples have：Silicon source material and
The combination of copper source material, the combining of copper source material and silver-colored source material, combination or silicon source material, the copper of silver-colored source material and silicon source material
Combination of source material and silver-colored source material etc..
Preferably, source of aluminium material includes any one in aluminium chloride, aluminum sulfate, aluminum nitrate or aluminum acetate or at least two
The combination planted, the combination is typical but non-limiting examples have：The group of the combination of aluminium chloride and aluminum sulfate, aluminum sulfate and aluminum nitrate
Conjunction, the combination of aluminum nitrate and aluminum acetate, the combination or aluminium chloride of aluminum acetate and aluminium chloride, the combination of aluminum sulfate and aluminum nitrate etc.,
More preferably aluminum nitrate and/or aluminium chloride.
Preferably, copper source material includes any one in copper nitrate, copper chloride, copper sulphate or copper acetate or at least two
The combination planted, the combination is typical but non-limiting examples have：The group of the combination of copper nitrate and copper chloride, copper chloride and copper sulphate
Conjunction, the combination of copper sulphate and copper acetate, the combination or copper nitrate of copper acetate and copper nitrate, the combination of copper chloride and copper sulphate etc.,
More preferably copper nitrate and/or copper sulphate.
Preferably, the silver-colored source material is silver nitrate.
As currently preferred technical scheme, step (1) described carbon source material is nano-sized carbon.
Preferably, the nano-sized carbon includes acetylene black and/or super pli.
The specific implementation step of step (1) of the present invention is by lithium source substance, manganese source substance and doping metals material and water
The mixed solution that three coexists is configured to, then mixes gained mixed solution with carbon source material, dries, that is, obtains presoma.
Wherein, the temperature of the drying be 40~200 DEG C, such as 46 DEG C, 55 DEG C, 67 DEG C, 70 DEG C, 75 DEG C, 89 DEG C, 100 DEG C,
120 DEG C, 134 DEG C, 150 DEG C, 180 DEG C etc., it is not limited to other unrequited numbers in cited numerical value, the number range
Value is equally applicable, preferably 80 DEG C.
As currently preferred technical scheme, step (2) presoma first obtained to step (1) that is sintered to is carried out
First sintering, then carry out the second sintering.
As currently preferred technical scheme, the temperature of first sintering is 150~450 DEG C, such as 150 DEG C, 200
DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C or 450 DEG C etc., it is not limited in cited numerical value, the number range other
Unrequited numerical value is equally applicable.
Preferably, the time of first sintering is 1~10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h
Deng it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, the temperature of second sintering is 550~900 DEG C, such as 550 DEG C, 600
DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or 900 DEG C etc., it is not limited to cited numerical value, the number range
Other interior unrequited numerical value are equally applicable.
Preferably, it is described second sintering time be 1~48h, such as 1h, 2h, 4h, 8h, 12h, 16h, 20h, 24h, 28h,
32h, 36h, 40h, 44h or 48h etc., it is not limited to other unrequited numerical value in cited numerical value, the number range
It is equally applicable.
The two of the object of the invention are to provide a kind of anode material for lithium-ion batteries, and the positive electrode is by any of the above-described kind
Preparation method is prepared.
Compared with prior art, the present invention at least has the advantages that：
(1) a kind of anode material for lithium-ion batteries for providing of the present invention, the positive electrode specific capacity, high rate performance and is followed
Ring performance shows excellent, and specific capacity is up to 102mAh/g (1C), and cycle-index is up to 300 times；
(2) a kind of preparation method for anode material for lithium-ion batteries that the present invention is provided, the preparation method is prepared
Positive electrode purity it is high；
(3) a kind of preparation method for anode material for lithium-ion batteries that the present invention is provided, the preparation method technique is simple,
It is easy to control, reproducible, cost is relatively low, the material good combination property of preparation, is easy to before large-scale production, practical application
Scape is wide.
Brief description of the drawings
Fig. 1-a are gained sample LiMn in embodiment 41.9Al0.1O4X-ray powder diffraction figure；
Fig. 1-b are gained sample LiMn in embodiment 41.9Al0.1O4Scanning electron microscope (SEM) photograph；
Fig. 1-c are gained sample LiMn in embodiment 41.9Al0.1O4High rate performance curve；
Fig. 2 is gained sample LiMn in embodiment 51.95Al0.05O4Scanning electron microscope (SEM) photograph；
Fig. 3 is gained sample LiMn in embodiment 61.9Al0.1O4Scanning electron microscope (SEM) photograph；
Fig. 4 is gained sample LiMn in embodiment 71.9Al0.1O4Scanning electron microscope (SEM) photograph；
Fig. 5 is gained sample LiMn in embodiment 81.9Al0.1O4Scanning electron microscope (SEM) photograph；
Fig. 6 is gained sample LiMn in embodiment 91.9Al0.1O4High rate performance curve；
Fig. 7 is gained sample LiMn in embodiment 101.9Al0.1O4Scanning electron microscope (SEM) photograph；
Fig. 8 is gained sample LiMn in embodiment 111.9Cu0.1O4Scanning electron microscope (SEM) photograph；
Fig. 9 is gained sample LiMn in comparative example 22O4Scanning electron microscope (SEM) photograph.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) manganese chloride, lithium oxalate, aluminium chloride and water are mixed, is configured to manganese nitrate, lithium nitrate and aluminum nitrate concentration difference
For 2.08mol/L, 1.18mol/L, 0.23mol/L mixed solution uniformly mixes mixed solution described in 8mL with 1g acetylene blacks
Close, mixture is dried in 200 DEG C of baking ovens, presoma is obtained；
(2) presoma for obtaining step (1) is warming up to 150 DEG C of sintering 10h, then is warming up to 550 DEG C of sintering 48h, cooling
To room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 2
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) manganous bromide, lithium acetate, aluminum sulfate and water are mixed, is configured to manganese nitrate, lithium nitrate and aluminum nitrate concentration difference
For 0.52mol/L, 0.31mol/L, 0.058mol/L mixed solution uniformly mixes mixed solution described in 8mL with 1g acetylene blacks
Close, mixture is dried in 40 DEG C of baking ovens, presoma is obtained；
(2) presoma for obtaining step (1) is warming up to 450 DEG C of sintering 1h, then is warming up to 700 DEG C of sintering 10h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 3
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) manganese oxalate, lithium hydroxide, aluminum acetate and water are mixed, is configured to manganese nitrate, lithium nitrate and aluminum nitrate concentration point
Not Wei 2.08mol/L, 1.18mol/L, 0.23mol/L mixed solution is equal by mixed solution described in 8mL and 1g super pli
Even mixing, mixture is dried in 80 DEG C of baking ovens, presoma is obtained；
(2) presoma for obtaining step (1) is warming up to 300 DEG C of sintering 5h, then is warming up to 800 DEG C of sintering 6h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 4
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 5
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.925mol/L, 1.6mol/L, 0.075mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene
Black uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 6
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 750 DEG C of sintering 8h, is cooled to room temperature, that is, obtains lithium ion battery
Positive electrode.
Embodiment 7
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminium chloride and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 8
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 1200 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 9
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 500 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 10
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, aluminum nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 0.7125mol/L, 0.4mol/L, 0.04mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene
Black uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Embodiment 11
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate, copper nitrate and water, be configured to manganese nitrate, lithium nitrate and aluminum nitrate
Concentration is respectively 2.85mol/L, 1.6mol/L, 0.15mol/L mixed solution, by mixed solution described in 8mL and 1g acetylene blacks
Uniform mixing, is heat-treated 4h for first 65 DEG C, then 80 DEG C of processing 1h, obtain presoma in an oven by mixture；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
Comparative example 1
A kind of preparation method of anode material for lithium-ion batteries, methods described except step (1) described mixed solution not with
Acetylene black mixing is outer, and other conditions are same as Example 1.
Comparative example 2
A kind of preparation method of anode material for lithium-ion batteries, the described method comprises the following steps：
(1) mixed with 50% manganese nitrate solution, lithium nitrate water, be configured to manganese nitrate and nitric acid lithium concentration respectively 3mol/
L, 1.6mol/L mixed solution, mixed solution described in 8mL is uniformly mixed with 1g acetylene blacks, by mixture in an oven first 65
DEG C heat treatment 4h, then 80 DEG C processing 1h, obtain presoma；
(2) presoma for obtaining step (1) is warming up to 350 DEG C of sintering 4h, then is warming up to 750 DEG C of sintering 8h, is cooled to
Room temperature, that is, obtain anode material for lithium-ion batteries.
The anode material for lithium-ion batteries that embodiment 1-11 and comparative example 1 and 2 are prepared, the hand protected in argon gas
Experiment fastening lithium ionic cell is assembled into casing, the specific capacity of above-mentioned lithium ion battery, high rate performance and cycle-index are entered
Row test, test result is as shown in table 1.
Table 1
As it can be seen from table 1 the experiment button that the anode material for lithium-ion batteries that embodiment 1-11 is prepared is assembled into
The specific capacity of lithium ion battery is 102 mAh/g (1C) to the maximum, and cycle-index is up to 300 times, and in the preparation process of comparative example 1
Acetylene black is not added, and the specific capacity of experiment fastening lithium ionic cell is only 33mAh/g (1C), and cycle-index is only 100 times, right
Ratio 2 is doping metals aluminium, and the specific capacity for causing fastening lithium ionic cell is only 52 mAh/g (1C), and cycle-index is only
200 times.
As shown in Fig. 2 the aluminium doping of embodiment 5 is the half of embodiment 4, porous spherical structure still can be obtained.Such as Fig. 3
Shown, because embodiment 6 does not carry out the first sintering, therefore the positive electrode prepared can not form spherical structure.Such as Fig. 5 institutes
Show, the pattern for the anode material for lithium-ion batteries that embodiment 8 is prepared occurs reuniting, is roughened, and this is due to the second burning
Caused by junction temperature is too high.As shown in fig. 6, the high rate performance for the anode material for lithium-ion batteries that embodiment 9 is prepared is low
In embodiment 4, this, which is due to that the second sintering temperature is too low, causes product crystallinity low, poor-performing.As shown in figure 8, when doping
When metal is copper, preparation-obtained positive electrode people can form chondritic.As shown in figure 9, because comparative example 2 is not added with
Doping metals, preparation-obtained positive electrode is discrete particles structure, it is impossible to form chondritic.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and being open.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method for preparing anode material of lithium-ion battery, it is characterised in that the described method comprises the following steps：
(1) lithium source substance, manganese source substance, doping metals material and carbon source material are mixed, obtains presoma；
(2) presoma for obtaining step (1) is sintered, and obtains anode material for lithium-ion batteries.
2. preparation method according to claim 1, it is characterised in that step (1) carbon source material and the lithium source thing
The mol ratio of matter is (5~20):1, be preferably (5~12):1.
3. preparation method according to claim 1 or 2, it is characterised in that step (1) described lithium source substance, manganese source substance
Mol ratio with doping metals material is (1.02~1.08):(2-x):X, wherein 0 ＜ x≤0.2.
4. the preparation method according to claim any one of 1-3, it is characterised in that the lithium source substance include lithium carbonate,
Any one in lithium hydroxide, lithia, lithium oxalate, lithium acetate or lithium nitrate or at least two combination；
Preferably, the manganese source substance include manganous bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, manganese sulfate or
Any one in manganese acetate or at least two combination.
5. the preparation method according to claim any one of 1-4, it is characterised in that step (1) the doping metals material
Combination including any one in silicon source material, copper source material or silver-colored source material or at least two；
Preferably, source of aluminium material includes any one in aluminium chloride, aluminum sulfate, aluminum nitrate or aluminum acetate or at least two
Combination, more preferably aluminum nitrate and/or aluminium chloride；
Preferably, copper source material includes any one in copper nitrate, copper chloride, copper sulphate or copper acetate or at least two
Combination, more preferably copper nitrate and/or copper sulphate；
Preferably, the silver-colored source material is silver nitrate.
6. the preparation method according to claim any one of 1-5, it is characterised in that step (1) described carbon source material is to receive
Rice carbon；
Preferably, the nano-sized carbon includes acetylene black and/or super pli.
7. the preparation method according to claim any one of 1-6, it is characterised in that step (2) is described to be sintered to first to step
Suddenly the presoma that (1) is obtained carries out first and sintered, then carries out the second sintering.
8. preparation method according to claim 7, it is characterised in that the temperature of first sintering is 150~450 DEG C；
Preferably, the time of first sintering is 1~10h.
9. the preparation method according to claim 7 or 8, it is characterised in that the temperature of second sintering is 550~900
℃；
Preferably, the time of second sintering is 1~48h.
10. a kind of anode material for lithium-ion batteries, it is characterised in that the positive electrode is as described in claim any one of 1-9
Preparation method is prepared.
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| CN110112411A (en) * | 2019-04-23 | 2019-08-09 | 上海应用技术大学 | A kind of MnCO3Microballoon and preparation method thereof |
| CN111525123A (en) * | 2020-04-29 | 2020-08-11 | 国家纳米科学中心 | Cathode material of water-based lithium ion battery and preparation method and application thereof |
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| CN103730654A (en) * | 2014-01-18 | 2014-04-16 | 南通瑞翔新材料有限公司 | High-capacity high-stability lithium manganate positive electrode material and preparation method thereof |
| CN103825017A (en) * | 2014-02-13 | 2014-05-28 | 宁波金和新材料股份有限公司 | Preparation method of lithium manganate used as lithium ion battery cathode material and doped lithium manganate |
| CN105161711A (en) * | 2015-09-08 | 2015-12-16 | 国家纳米科学中心 | Lithium manganate cathode material, preparation method and use |
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| CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
| CN103730654A (en) * | 2014-01-18 | 2014-04-16 | 南通瑞翔新材料有限公司 | High-capacity high-stability lithium manganate positive electrode material and preparation method thereof |
| CN103825017A (en) * | 2014-02-13 | 2014-05-28 | 宁波金和新材料股份有限公司 | Preparation method of lithium manganate used as lithium ion battery cathode material and doped lithium manganate |
| CN105161711A (en) * | 2015-09-08 | 2015-12-16 | 国家纳米科学中心 | Lithium manganate cathode material, preparation method and use |
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| CN110112411A (en) * | 2019-04-23 | 2019-08-09 | 上海应用技术大学 | A kind of MnCO3Microballoon and preparation method thereof |
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