CN106252594B - A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure - Google Patents
A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure Download PDFInfo
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure, the invention belongs to lithium ion battery material and its manufacturing process technology fields, and in particular to a kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure.The problem of that the purpose of the present invention is to solve conventional lithium-ion battery positive electrode specific capacities is low, cycle life is short and charging/discharging voltage window narrows.The ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of Co deposited synthesis of the present invention is made of two phase material, and the phase in the two-phase is Li2MnO3Phase, another phase are stratiform LiMO2Phase.It is of the invention the preparation method comprises the following steps: the configuration of one, solution, two, react the preparation of bottom liquid, three, the preparation of presoma, four, high temperature process heat.Material prepared by the present invention is used for anode material for lithium-ion batteries.
Description
Technical field
The invention belongs to lithium ion battery material and its manufacturing process technology fields, and in particular to a kind of has nanoscale
The ball-shaped lithium-ion battery anode material and its synthetic method of two-phase coexistent structure.
Background technique
The increasingly aggravation of the violent consumption and environmental problem of fossil energy, has promoted people to clean energy resource and power-saving technology
Pursuit, battery is the important medium of reasonable energy utilization as the device that a kind of chemical energy and electric energy mutually convert.Compared to
Traditional one-shot battery and using plumbic acid, ni-Cd as the secondary cell of representative, energy density is high, the circulation longevity with having for lithium ion battery
The advantages such as life is long, environment compatibility is good, light-weight, small in size, can be widely used in mobile communication and digital product, electronic work
The fields such as tool, new-energy automobile, renewable energy energy storage, smart grid peak-clipping and valley-filling can also be led in Aeronautics and Astronautics, military affairs etc.
Domain plays a significant role, and is the novel green electrochmical power source greatly developed both at home and abroad.
Currently, the key for developing high performance lithium ion battery is positive electrode.In the hair of lithium ion battery more than two decades
In exhibition course, positive electrode development slowly becomes the bottleneck for hindering high-capacity lithium ion cell development relatively.Compared to cathode material
Expect 300mAh/g or more specific capacity, the low capacity of positive electrode just become restrict performance of lithium ion battery further promoted it is short
Plate.In addition, positive electrode also plays main function to critical natures such as the operating voltage and capacities, stability and cost of battery.Reason
The anode material for lithium-ion batteries thought should have high capacity, high output current potential, good high rate performance and cyclical stability, low cost
And the features such as environmental-friendly.
Currently, the positive electrode of various systems it is still different degrees of there are it is certain the shortcomings that, it is difficult to while on meeting
State and required, the anode material for lithium-ion batteries of common reporter mainly have the embedding de- oxidate for lithium of stratiform, spinel oxide and
The polyanionic material of olivine structural.Li2MnO3It is the highest compound of Li/Mn ratio in manganese oxygen based compound, has similar
In LiCoO2Layer structure.The study found that Li2MnO3Stablizing stratiform LiMO2The side such as cathode material structure and contribution capacity
Face plays key player.If Li2MnO3In 2 Li+All abjections, capacity are up to 458mAh/g, but due to being in eight
The Mn of face body oxygen environment is+4 valences, is difficult to be oxidized to higher price, and lithium ion is not easy deintercalation, thus early stage researches show that
Li2MnO3There is no electro-chemical activity.Robertson in 2002 etc. has found in high blanking voltage Li2MnO3Can with electrochemical activation,
The Li when charging voltage is higher than 4.5V2MnO3It is activated by electrochemistry, charging/discharging voltage platform occurs in 4.5V；And work as charging voltage
Li when lower than 4.5V2MnO3For electrochemicaUy inert, it is not involved in redox reaction.In view of Li2MnO3The above property of material, this
Invention makes coprecipitation process is synchronous with redox synthesis process to carry out by simple effective method, and then two kinds anti-
Product is answered uniformly to reunite with obtaining altogether and spherical or spherical there is nanoscale Li2MnO3Particle and anode material for lithium-ion batteries
The equally distributed anode material for lithium-ion batteries of primary particle obtains while having high capacity, high circulation stability and height to fill
The anode material for lithium-ion batteries of discharge voltage window.
Summary of the invention
That the purpose of the present invention is to solve conventional lithium-ion battery positive electrode specific capacities is low, cycle life is short and fills
The problem of discharge voltage window narrows, and a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure is provided
Material and its synthetic method.
Ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of the invention is made of two phase material,
A phase in the two-phase is Li2MnO3Phase, another phase are stratiform LiMO2Phase, M Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr,
One of Fe, Ti, Cu, Mo metal or a variety of combinations.
The synthetic method of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of the invention press with
Lower step carries out:
One, the configuration of solution: be respectively configured concentration be 0.01mol/L~2mol/L potassium permanganate solution a,
Precipitating reagent aqueous solution b, 0.02mol/L~15mol/L complexing agent aqueous solution c, 0.01mol/L of 0.01mol/L~5mol/L
The mixed metal saline solution d and concentration of~4mol/L is 0.01mol/L~4mol/L manganous salt aqueous solution e；
Two, react bottom liquid preparation: by complexing agent aqueous solution c with deionized water be diluted to concentration be 0.01mol/L~
The aqueous solution f of 5mol/L, and aqueous solution f is added in the Liquid-phase reactor persistently stirred as initial reaction bottom liquid；
Three, the preparation of presoma: 35 DEG C~85 DEG C of the reaction temperature and pH value 6.5~12 of reaction system are controlled, will be mixed
Aqueous metal salt d, precipitating reagent aqueous solution b and complexing agent aqueous solution c are with 1:(0.1~10): the feed rate ratio of (0.1~10)
It is injected in the Liquid-phase reactor continuously stirred simultaneously, while under stirring by potassium permanganate solution a and bivalent manganese salt water
Solution e is with 1:(0.01~100) molar ratio be added in the Liquid-phase reactor that continuously stirs, sufficiently reaction generates MnO2Nanometer
Grain, the revolving speed of the Liquid-phase reactor are 300r/min~1000r/min；And then in the work of complexing agent in coprecipitation reaction kettle
With lower MnO2The nanometer primary particle that nano particle is generated with transition metal co-precipitation is mutually uniformly reunited；To anti-in reaction process
System is answered to be timed intermittent overflow or continuity overflow to control the constant of overall reaction liquid product in reaction system；It is anti-
Only MnO2It is unevenly distributed phenomenon caused by the independent reunion of nano particle, supersonic generator can be introduced in the reaction system
Aid dispersion；
It is down to room temperature naturally after reaction, then reaction product is filtered and dried after multiple deionized water lotion
Dry, drying temperature≤200 DEG C are obtained with MnO2Particle and coprecipitated product primary particle M (OH)2Nanoscale two-phase coexistent
Precursor of lithium ionic cell positive material；
Overflow manner is depending on the actual requirement to Granularity Distribution.The intermittent overflow of timing is suitble to produce in batches
Process, concrete operation method are to stop reaction feed when reacting every progress 1h~10h, after the sedimentation of reaction product solid, are opened
Flow spill valve releases supernatant liquor, and the supernatant liquid measure released every time is consistent with the liquid inlet volume in this time, the supernatant that overflow goes out
Reaction product is not contained in liquid；Continuity overflow is suitble to continuous uninterrupted production process, concrete operation method be according to react into
Enter the amount of liquid how much adjusting overflows of amount of liquid go out, so that total amount of liquid is kept constant in reaction kettle, the supernatant that overflow goes out
In include reaction product.
Four, high temperature process heat: by obtained precursor of lithium ionic cell positive material and lithium source by 1:1~1:1.3's
Molar ratio is mixed and stirred for obtaining solid mixture in 10~60 minutes；It is then transferred in saggar and is compacted, in atmosphere sintering
In furnace, 3~10h is kept the temperature at temperature T1, then proceedes to be warming up to temperature T2 and 5~30h of high temperature sintering is carried out at temperature T2,
React lithium source sufficiently with persursor material, temperature T1 is 450 DEG C~700 DEG C, and temperature T2 is 700 DEG C~1000 DEG C；Reaction knot
It is down to room temperature after beam and is crushed, is sieved, finally obtains with stratiform LiMO2Or and Li2MnO3The nanoscale two-phase coexistent knot of particle
The ball-shaped lithium-ion battery anode material of structure.
The mixed salt solution is metal hydrochloride, metal nitrate, metal sulfate, one in metal acetate salt
Kind or a variety of combinations；The metal of the mixed salt solution be Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu,
One of Mo or a variety of combinations.
Complexing agent in the complexing agent aqueous solution is ammonium hydroxide, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, lemon
One of lemon acid ammonium, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, malonic acid or in which several
The combination of kind；
Precipitating reagent in the precipitating reagent aqueous solution is ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, carbon
One of sour potassium, lithium carbonate or in which several combinations.
The lithium source be lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate lithium hydroxide, lithium sulfate, lithium chloride, lithium fluoride,
One of lithium oxalate, lithium phosphate, lithium hydrogen phosphate or a variety of mixtures.
Feed rate according to the actual demand to reactor product composition than being calculated.Wherein potassium permanganate and manganous salt
Ratio according to potassium permanganate and manganous salt carry out redox reaction chemical reaction ratio and design product lithium from
Mn in sub- cell positive material4+With Mn3+Content ratio and determine.Manganese salt and the ratio of other transition metal are set according to product
It counts desired content ratio of the manganese element in product anode material for lithium-ion batteries and is calculated.The feed rate of complexing agent
So that complexing agent concentration is that 0mol/L~2mol/L is advisable in reaction system.The feed rate of precipitating reagent is according to reaction to pH's
Demand is pH control to be advisable between 6.5~12.
The present invention passes through control MnO2The synthesis of nano particle and the co-precipitation process of transition metal, reach MnO2Nanometer
Grain is mutually reunited altogether with coprecipitated product nanometer primary particle synchronized compound and by molecular weak interaction, and then is formed spherical
Or spherical precursor of lithium ionic cell positive material second particle, it is then sufficiently mixed simultaneously high temperature sintering system with lithium source
There must be the ball-shaped lithium-ion battery anode material of nanoscale two-phase coexistent structure.The method of the present invention can effectively prevent MnO2It receives
Rice grain or coprecipitated product nanometer primary particle are individually reunited, and obtain total reunion secondary that two kinds of particles are evenly distributed
Grain product.The method of the present invention is easy to operate simultaneously, is convenient for large-scale production application, anode material for lithium-ion batteries obtained
With high specific capacity, good cyclical stability and wide charging/discharging voltage window.
The present invention compared with the existing technology the advantages of:
1. it is same that the method for the present invention can effectively control coprecipitation process and redox synthesis process in reaction process
Step carries out, the MnO that control redox reaction generates2The M (OH) that the coprecipitation reaction of nano particle and transition metal generates2It receives
Rice grain is uniformly mutually reunited, and then forms the spherical or spherical lithium ion battery with nanoscale two-phase coexistent structure just
Pole material precursor second particle.
2. the method for the present invention can control any Mn of synthesis4+/Mn3+Ratio and content have nanoscale two-phase coexistent knot
The anode material for lithium-ion batteries of structure.Mn in product can be effectively controlled by the ratio of control potassium permanganate and manganous salt4+
With Mn3+Ratio, manganese element can effectively be controlled in product lithium by control manganese element and the charge proportions of other transition metal
Content in ion battery positive electrode.Pass through Mn in regulation product4+/Mn3+Ratio and content, which can get, meets different product
The anode material for lithium-ion batteries that energy (capacity, multiplying power, circulation etc.) requires.
3. the anode material for lithium-ion batteries with nanoscale two-phase coexistent structure of the method for the present invention synthesis, wherein Mn4+
With nanoscale Li2MnO3Form individually at mutually existing, Li2MnO3Presence can during charge and discharge cycles stabilizing material
Structure, improve cycle performance, and the charging/discharging voltage window of material can be widened.When charge cutoff voltage is 4.5V or less
Li2MnO3Material is not involved in any electrochemical reaction, can play the role of skeletal support, and effective stabilizing material structure promotes material
Cycle performance.When charge cutoff voltage is higher than 4.5V, Li2MnO3Start gradually to activate and release chemical property, substantially
Promote the volumetric properties of material.25 DEG C, when 3~4.5V, 5~20mAh/g of capacity boost.
4. the method for the present invention is simple and easy to do, the synthesis of material passes through relatively simple coprecipitation reaction and redox reaction
Collaboration carries out, and can sufficiently simplify production technology, reduces production energy consumption, is convenient for continuous industrialized production,
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of precursor of lithium ionic cell positive material in embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure of sintered anode material for lithium-ion batteries in embodiment 1.
Fig. 3 is sintered anode material for lithium-ion batteries XRD diagram in embodiment 1.
Fig. 4 is sintered anode material for lithium-ion batteries 3-4.3V first charge-discharge curve graph in embodiment 1.
Fig. 5 is sintered anode material for lithium-ion batteries 3-4.3V cycle performance curve graph in embodiment 1.
Fig. 6 is sintered anode material for lithium-ion batteries 3-4.5V first charge-discharge curve graph in embodiment 1.
Fig. 7 is sintered anode material for lithium-ion batteries 3-4.5V cycle performance curve graph in embodiment 1.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the ball-shaped lithium-ion battery with nanoscale two-phase coexistent structure of present embodiment is just
Pole material is made of two phase material, and the phase in the two-phase is Li2MnO3Phase, another phase are stratiform LiMO2Phase, M Ni, Co,
One of Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo metal or a variety of combinations.
Specific embodiment 2: the spherical lithium with nanoscale two-phase coexistent structure as described in specific embodiment one from
The synthetic method of sub- cell positive material sequentially includes the following steps:
One, the configuration of solution: be respectively configured concentration be 0.01mol/L~2mol/L potassium permanganate solution a,
Precipitating reagent aqueous solution b, 0.02mol/L~15mol/L complexing agent aqueous solution c, 0.01mol/L of 0.01mol/L~5mol/L
The mixed metal saline solution d and concentration of~4mol/L is 0.01mol/L~4mol/L manganous salt aqueous solution e；
Two, react bottom liquid preparation: by complexing agent aqueous solution c with deionized water be diluted to concentration be 0.01mol/L~
The aqueous solution f of 5mol/L, and aqueous solution f is added in the Liquid-phase reactor persistently stirred as initial reaction bottom liquid；
Three, the preparation of presoma: 35 DEG C~85 DEG C of the reaction temperature and pH value 6.5~12 of reaction system are controlled, will be mixed
Aqueous metal salt d, precipitating reagent aqueous solution b and complexing agent aqueous solution c are with 1:(0.1~10): the feed rate ratio of (0.1~10)
It is injected in the Liquid-phase reactor continuously stirred simultaneously, while under stirring by potassium permanganate solution a and bivalent manganese salt water
Solution e is with 1:(0.01~100) molar ratio be added in the Liquid-phase reactor that continuously stirs, the revolving speed of the Liquid-phase reactor is
300r/min~1000r/min；Reaction process keeps reaction solution constant total volume；It is down to room temperature naturally after reaction, then
Reaction product is filtered and dried after 3 times~5 times deionized waters are washed, drying temperature≤200 DEG C obtain lithium ion battery
Positive electrode material precursor；
Four, high temperature process heat: by obtained precursor of lithium ionic cell positive material and lithium source by 1:(1~1.3)
Molar ratio is mixed and stirred for obtaining solid mixture in 10~60 minutes；It is then transferred in saggar and is compacted, in atmosphere sintering
In furnace, 3~10h is kept the temperature at 450 DEG C~700 DEG C of temperature, then proceed to be warming up to 700 DEG C~1000 DEG C and 700 DEG C~
5~30h of high temperature sintering is carried out at 1000 DEG C, reacts lithium source sufficiently with persursor material；It is down to room temperature after reaction and breaks
Broken, sieving, finally obtains with stratiform LiMO2And Li2MnO3The ball-shaped lithium-ion battery of the nanoscale two-phase coexistent structure of particle
Positive electrode.
Specific embodiment 3: present embodiment is unlike specific embodiment two, reaction process described in step 3
Keeping reaction solution constant total volume is realized by the intermittent overflow of timing or continuity overflow；The timing intermittence overflow
Concrete operation method is to stop reaction feed when reacting every progress 1h~10h, after the sedimentation of reaction product solid, opens overflow
Valve releases supernatant liquor, and the supernatant liquid measure released every time is consistent with the liquid inlet volume in this time, in the supernatant that overflow goes out
Without containing reaction product；How much adjusting overflows that amount of liquid is reacted into according to the continuity overflow concrete operation method go out
Amount of liquid so that total amount of liquid is kept constant in reaction kettle include reaction product in the supernatant that overflow goes out.Other steps
It is identical with embodiment two with parameter.
Specific embodiment 4: present embodiment unlike specific embodiment two, is in step 3 reaction process
Prevent MnO2It is unevenly distributed phenomenon caused by the independent reunion of nano particle, it is auxiliary to introduce supersonic generator in the reaction system
Help dispersion.Other steps are identical with embodiment two with parameter.
Specific embodiment 5: present embodiment is unlike specific embodiment two, the mixed salt solution
For one of metal hydrochloride, metal nitrate, metal sulfate, metal acetate salt or a variety of combinations；The mixing gold
The metal for belonging to salting liquid is one of Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo or a variety of combinations.Its
He is identical with embodiment two step with parameter.
Specific embodiment 6: present embodiment is unlike specific embodiment two, in the complexing agent aqueous solution
Complexing agent be ammonium hydroxide, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride,
One of tartaric acid, maleic acid, succinic acid, citric acid, malonic acid or in which several combinations.Other steps and parameter and tool
Body embodiment two is identical.
Specific embodiment 7: present embodiment is unlike specific embodiment two, in the precipitating reagent aqueous solution
Precipitating reagent be one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate or in which
Several combinations.Other steps are identical with embodiment two with parameter.
Specific embodiment 8: present embodiment is unlike specific embodiment two, the lithium source be lithium hydroxide,
Lithium carbonate, lithium nitrate, lithium acetate lithium hydroxide, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, in lithium hydrogen phosphate
One or more mixtures.Other steps are identical with embodiment two with parameter.
Specific embodiment 9: present embodiment is unlike specific embodiment two, atmosphere sintering described in step 4
Atmosphere in furnace is O2Or air.Other steps are identical with embodiment two with parameter.
Embodiment one
Firstly, preparing the nickel sulfate and cobaltous sulfate mixed metal that molar ratio is Ni:Co=8:1 and total concentration is 2.0mol/L
Salting liquid, the complexing agent ammonia spirit of 3.0mol/L, the precipitating reagent sodium hydroxide solution of 2.0mol/L, the ammonium hydroxide of 0.5mol/L are molten
Liquid, the KMnO of 2mol/L4Solution, the manganese sulfate solution of 2.0mol/L.
Then the ammonia spirit for taking the complexing agent ammonia spirit of 3.0mol/L to be diluted to 0.5mol/L will as reaction bottom liquid
It is added in reaction kettle.
In inert N2It is then that mixed salt solution, ammonium hydroxide is molten by reaction bottom liquid heat to 50 DEG C under atmosphere protection
Liquid, sodium hydroxide solution are gradually added high-speed stirred (800r/ with the speed ratio of 1.0mL/min:1.0mL/min:5mL/min
Min in reaction kettle), while making KMnO4Solution and manganese sulfate solution, which sufficiently react, generates nanometer MnO2Particle and with co-precipitation
Product is reunited altogether.The pH of entire reaction system is controlled 11, and carries out primary overflow to keep reaction solution being volume 1.5L every 1h,
Coreaction 15 hours.
After after the reaction was completed, 5 soluble impurities removed in material are cleaned with deionized water, are then filtered, in vacuum
Under the conditions of 120 DEG C of drying materials, obtain precursor of lithium ionic cell positive material powder.
Precursor of lithium ionic cell positive material powder 25g, a hydronium(ion) lithia 12.0g are weighed, is mixed and stirred for 30
Minute, it is then transferred in corundum porcelain boat and is compacted.Then it is transferred in atmosphere sintering furnace, under oxygen atmosphere, with 2
DEG C/heating rate of min is warming up to 500 DEG C and keeps the temperature 5h at 500 DEG C, it then heats to 800 DEG C and is kept the temperature at 800 DEG C
15h reacts lithium hydroxide sufficiently with persursor material, obtains the spherical lithium ion with nanoscale two-phase coexistent structure
Cell positive material 0.1Li2MnO3·0.9LiNi0.8Co0.1O2。
Test result shows: as shown in figure 1 shown in the scanning electron microscope (SEM) photograph (SEM) of persursor material, persursor material primary
Grain be in flaky nanometer structure, second particle be it is spherical, average-size be 7.2 μm；Sintered lithium ion cell positive in Fig. 2
Shown in scanning electron microscope (SEM) figure of material, material primary particle is that nanometer is blocky after sintering, and second particle is still spherical；
By the XRD test of Fig. 3, it can be concluded that, the sintered material in the present embodiment has good Lamellar character, and free from admixture phase
In the presence of；By in Fig. 4 25 DEG C it can be seen from first charge-discharge curve, when 3V~4.3V, first charge-discharge recycles coulombic efficiency
88.8%, first discharge specific capacity 203.8mAh/g；By 1C (200mA/g) it can be seen from cycle performance test curve in Fig. 5
Capacity is 178.4mAh/g under multiplying power, and 100 circulation volume conservation rates are 96.2% under 1C (200mA/g) multiplying power.By Fig. 6 and Fig. 7
Middle first charge-discharge curve and cycle performance curve can be seen that 25 DEG C, and when 3V~4.5V, first charge-discharge recycles coulombic efficiency
86.9%, capacity is 200.9mAh/g, 1C (200mA/ under first discharge specific capacity 218.5mAh/g, 1C (200mA/g) multiplying power
G) 100 circulation volume conservation rates are 74.2% under multiplying power.
Claims (8)
1. a kind of synthetic method of the ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure: its feature exists
In: this method sequentially includes the following steps:
One, potassium permanganate solution a, 0.01mol/L that concentration is 0.01mol/L~2mol/L the configuration of solution: is respectively configured
Precipitating reagent aqueous solution b, 0.02mol/L~15mol/L complexing agent aqueous solution c, 0.01mol/L~4mol/L of~5mol/L
Mixed metal saline solution d and concentration are 0.01mol/L~4mol/L manganous salt aqueous solution e；
Two, react the preparation of bottom liquid: it is 0.01mol/L~5mol/L that complexing agent aqueous solution c, which is diluted to concentration with deionized water,
Aqueous solution f, and aqueous solution f is added in the Liquid-phase reactor that persistently stirs as initial reaction bottom liquid；
Three, the preparation of presoma: 35 DEG C~85 DEG C of the reaction temperature and pH value 6.5~12 of reaction system are controlled, by mixed metal
Saline solution d, precipitating reagent aqueous solution b and complexing agent aqueous solution c are with 1:(0.1~10): the feed rate ratio of (0.1~10) is simultaneously
It injects in the Liquid-phase reactor continuously stirred, while under stirring by potassium permanganate solution a and manganous salt aqueous solution e
With 1:(0.01~100) molar ratio be added in the Liquid-phase reactor that continuously stirs, the revolving speed of the Liquid-phase reactor is 300r/
Min~1000r/min；Reaction process keeps reaction solution constant total volume；It is down to room temperature naturally after reaction, it then will reaction
Product is filtered and is dried, drying temperature≤200 DEG C after 3 times~5 times deionized waters are washed, and obtains lithium ion cell positive material
Material precursor；
Four, high temperature process heat: by obtained precursor of lithium ionic cell positive material and lithium source by 1:(1~1.3) mole
Solid mixture is obtained than being mixed and stirred for 10~60 minutes；It is then transferred in saggar and is compacted, in atmosphere sintering furnace,
3~10h is kept the temperature at 450 DEG C~700 DEG C of temperature, then proceedes to be warming up to 700 DEG C~1000 DEG C and at 700 DEG C~1000 DEG C
5~30h of high temperature sintering is carried out, reacts lithium source sufficiently with persursor material；It is down to room temperature after reaction and is crushed, is sieved,
It finally obtains with stratiform LiMO2And Li2MnO3The ball-shaped lithium-ion battery anode material of the nanoscale two-phase coexistent structure of particle
Material；
The ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure is made of two phase material, the two-phase
In a phase be Li2MnO3Phase, another phase are stratiform LiMO2Phase, M Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu,
One of Mo metal or a variety of combinations.
2. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: reaction process described in step 3, which keeps reaction solution constant total volume, is overflow by the way that timing is intermittent
What stream or continuity overflow were realized；The timing intermittence overflow concrete operation method is to stop when reacting every progress 1h~10h
Reaction feed, after reaction product solid sedimentation after, open flow spill valve release supernatant liquor, the supernatant liquid measure released every time with should
Liquid inlet volume in the section time is consistent, and reaction product is not contained in the supernatant that overflow goes out；Continuity overflow concrete operations side
The amount of liquid how much adjusting overflows of amount of liquid go out is reacted into according to method, so that total amount of liquid is kept constant in reaction kettle,
It include reaction product in the supernatant that overflow goes out.
3. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: being to prevent MnO in step 3 reaction process2Distribution caused by the independent reunion of nano particle is not
Uniform phenomenon introduces supersonic generator aid dispersion in the reaction system.
4. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: the metal salt in the mixed metal saline solution is metal hydrochloride, metal nitrate, gold
Belong to one of sulfate, metal acetate salt or a variety of combinations；The metal of the mixed metal saline solution be Ni, Co, Mn,
One of Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo or a variety of combinations.
5. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: the complexing agent in the complexing agent aqueous solution is ammonium hydroxide, ammonium chloride, ammonium nitrate, ammonium sulfate, vinegar
Sour ammonium, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, in malonic acid
A kind of or in which several combination.
6. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: the precipitating reagent in the precipitating reagent aqueous solution is ammonium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
One of lithium, sodium carbonate, potassium carbonate, lithium carbonate or in which several combinations.
7. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: the lithium source be lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium sulfate,
One of lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate or a variety of mixtures.
8. a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure according to claim 1
Synthetic method: it is characterized by: the atmosphere in atmosphere sintering furnace described in step 4 is O2Or air.
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