CN106252594A - A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure and synthetic method thereof - Google Patents
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure and synthetic method thereof Download PDFInfo
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- CN106252594A CN106252594A CN201610803039.6A CN201610803039A CN106252594A CN 106252594 A CN106252594 A CN 106252594A CN 201610803039 A CN201610803039 A CN 201610803039A CN 106252594 A CN106252594 A CN 106252594A
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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
- H01M4/131—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 with nanoscale two-phase coexistent structure and synthetic method thereof, the invention belongs to lithium ion battery material and manufacturing process technology field thereof, be specifically related to a kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure and synthetic method thereof.Conventional lithium-ion battery positive electrode specific capacity is low, cycle life is short and the problem of charging/discharging voltage window narrows to the invention aims to solution.The ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of Co deposited synthesis of the present invention is made up of two phase material, described biphase in a phase be Li2MnO3Phase, another phase is stratiform LiMO2Phase.The preparation method of the present invention is: one, the configuration of solution, two, the preparation of reaction end liquid, three, the preparation of presoma, four, high temperature process heat.Material prepared by the present invention is for anode material for lithium-ion batteries.
Description
Technical field
The invention belongs to lithium ion battery material and manufacturing process technology field thereof, be specifically related to a kind of there is nanoscale
The ball-shaped lithium-ion battery anode material of two-phase coexistent structure and synthetic method thereof.
Background technology
Acutely consuming and the day by day aggravation of environmental problem of fossil energy, has promoted people to clean energy resource and power-saving technology
Pursuit, battery is as the important medium that the device that a kind of chemical energy and electric energy mutually convert is reasonable energy utilization.Compared to
Tradition one-shot battery and the secondary cell with plumbic acid, NI-G as representative, lithium ion battery has energy density height, circulation longevity
The advantages such as life is long, environment compatibility is good, lightweight, volume is little, can be widely used in mobile communication and digital product, electronic work
The fields such as tool, new-energy automobile, regenerative resource energy storage, intelligent grid peak-clipping and valley-filling, also can lead in Aeronautics and Astronautics, military affairs etc.
Territory plays a significant role, and is the novel green electrochmical power source greatly developed both at home and abroad.
Currently, that develops high performance lithium ion battery it is critical only that positive electrode.Sending out at lithium ion battery more than two decades
In exhibition course, positive electrode development the most slowly becomes the bottleneck hindering high-capacity lithium ion cell development.Compared to negative pole material
Material more than 300mAh/g specific capacity, the low capacity of positive electrode just becoming restriction performance of lithium ion battery promote further short
Plate.Additionally, the critical natures such as running voltage, capacity, stability and the cost of battery are also played Main Function by positive electrode.Reason
The anode material for lithium-ion batteries thought should possess high power capacity, high output current potential, good high rate performance and cyclical stability, low cost
With features such as environmental friendliness.
At present, the existence the most in various degree of the positive electrode of various systems certain shortcoming, it is difficult to simultaneously meet on
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 compound that in manganese oxygen based compound, Li/Mn ratio is the highest, has similar
In LiCoO2Layer structure.Research finds, Li2MnO3In stable stratiform LiMO2The sides such as cathode material structure and contribution capacity
Face plays key player.If Li2MnO3In 2 Li+All abjections, its capacity is up to 458mAh/g, but owing to being in eight
The Mn of face body oxygen environment is+4 valencys, is difficult to be oxidized to more expensive state, and lithium ion is difficult to deintercalation, therefore research display in early days
Li2MnO3There is no electro-chemical activity.Robertson in 2002 etc. find at high blanking voltage Li2MnO3Can with electrochemical activation,
The Li when charging voltage is higher than 4.5V2MnO3Activated by electrochemistry, at 4.5V, charging/discharging voltage platform occurs；And work as charging voltage
Less than Li during 4.5V2MnO3For electrochemicaUy inert, it is not involved in redox reaction.In view of Li2MnO3The above character of material, this
Invent and by simple effective method, coprecipitation process is Tong Bu carried out, and then two kinds anti-with oxidoreduction building-up process
Answer product reunite altogether uniformly obtain spherical or class spherical there is nanoscale Li2MnO3Granule and anode material for lithium-ion batteries
The equally distributed anode material for lithium-ion batteries of primary particle, it is thus achieved that there is high power capacity, high cyclical stability and height simultaneously and fill
The anode material for lithium-ion batteries of discharge voltage window.
Summary of the invention
Conventional lithium-ion battery positive electrode specific capacity is low, cycle life is short and fills to the invention aims to solution
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 synthetic method thereof.
The ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of the present invention is made up of two phase material,
Described biphase in a phase be Li2MnO3Phase, another phase is stratiform LiMO2Phase, M is Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr,
The combination of one or more in Fe, Ti, Cu, Mo metal.
The method of the ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure of the present invention is by following step
Suddenly carry out:
One, the configuration of solution: be respectively configured potassium permanganate solution a that concentration is 0.01mol/L～2mol/L,
Complexing agent aqueous solution c, 0.01mol/L of precipitant aqueous solution b, 0.02mol/L～15mol/L of 0.01mol/L～5mol/L
～the hybrid metal saline solution d of 4mol/L and concentration are 0.01mol/L～4mol/L manganous salt aqueous solution e；
Two, react end liquid preparation: complexing agent aqueous solution c deionized water is diluted to concentration be 0.01mol/L～
The aqueous solution f of 5mol/L, and aqueous solution f is added in continuously stirred Liquid-phase reactor as liquid at the bottom of initial reaction；
Three, the preparation of presoma: control reaction temperature 35 DEG C～85 DEG C and the pH value 6.5～12 of reaction system, will mixing
Aqueous metal salt d, precipitant 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 simultaneously in the Liquid-phase reactor of continuous stirring, the most under stirring by potassium permanganate solution a and bivalent manganese saline
Solution e is with 1:(0.01～100) mol ratio add in the Liquid-phase reactor of continuous stirring, fully reaction generates MnO2Nanometer
Grain, the rotating speed of described Liquid-phase reactor is 300r/min～1000r/min；And then at the work of chelating agent in coprecipitation reaction still
Use lower MnO2The nanometer primary particle that nano-particle produces with transition metal co-precipitation is the most uniformly reunited；To instead in course of reaction
Answer system to be timed intermittent overflow or seriality overflow thus control long-pending constant of overall reaction liquid in reaction system；It is anti-
Only MnO2The skewness phenomenon caused of individually reuniting of nano-particle, can introduce excusing from death wave producer in reaction system
Aid dispersion；
Reaction is down to room temperature after terminating naturally, then product is filtered after repeatedly deionized water lotion and dries
Dry, dry temperature≤200 DEG C, obtain that there is MnO2Granule and coprecipitated product primary particle M (OH)2Nanoscale two-phase coexistent
Precursor of lithium ionic cell positive material；
Depending on overflow manner is according to the actual requirement to Granularity Distribution.The intermittent overflow of timing is suitable for producing in batches
Process, concrete operation method is for often carrying out 1h～10h when reaction, and stopped reaction feeds, and after the sedimentation of question response product solid, opens
Flow spill valve releases the supernatant, and the supernatant liquid measure every time released is consistent with the liquid inlet volume in this period, the supernatant that overflow goes out
Liquid does not contains product；Seriality overflow is suitable for continuously uninterrupted production process, react according to concrete operation method into
Enter the amount of liquid how many regulation overflows of amount of liquid go out so that in reactor, total amount of liquid keeps constant, that overflow goes out supernatant
In include product.
Four, high temperature process heat: by the precursor of lithium ionic cell positive material that obtains with lithium source by 1:1's～1:1.3
Mixed in molar ratio also stirs 10～60 minutes and obtains solid mixture；It is then transferred in saggar compacting, in atmosphere sintering
In stove, at temperature T1, it is incubated 3～10h, then proceedes to be warming up to temperature T2 and at temperature T2, carry out high temperature sintering 5～30h,
Making lithium source fully react 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 bundle and crushes, sieve, finally giving and there is stratiform LiMO2Or and Li2MnO3The nanoscale two-phase coexistent knot of granule
The ball-shaped lithium-ion battery anode material of structure.
Described mixed salt solution is in slaine hydrochlorate, metal nitrate, metal sulfate, metal acetate salt
Kind or multiple combination；The metal of described mixed salt solution is Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu,
The combination of one or more in Mo.
Chelating agent in described complexing agent aqueous solution is ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, lemon
A kind of or the most several in lemon acid ammonium, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, malonic acid
The combination planted；
Precipitant in described precipitant aqueous solution is ammonia, sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate, carbon
A kind of or the most several combination in acid potassium, lithium carbonate.
Described lithium source be Lithium hydrate, lithium carbonate, lithium nitrate, lithium acetate Lithium hydrate, lithium sulfate, lithium chloride, lithium fluoride,
The mixture of one or more in lithium oxalate, lithium phosphate, lithium hydrogen phosphate.
Feed rate is calculated than according to the actual demand forming reactor product.Wherein potassium permanganate and manganous salt
Ratio according to potassium permanganate and manganous salt carry out the chemical reaction ratio of redox reaction and the product lithium of design from
Mn in sub-cell positive material4+With Mn3+Content ratio and determine.Manganese salt sets according to product with the ratio of other transition metal
Count the manganese element required content ratio in product anode material for lithium-ion batteries and be calculated.The feed rate of chelating agent
It is advisable so that reaction system complexing agent concentration is 0mol/L～2mol/L.The feed rate of precipitant is according to reacting pH's
Demand is to control pH to be advisable between 6.5～12.
The present invention is by controlling MnO2The synthesis of nano-particle and the co-precipitation process of transition metal, reach MnO2Nanometer
Grain and coprecipitated product nanometer primary particle synchronized compound also rely on molecular weak interaction to reunite mutually altogether, and then formed spherical
Or the precursor of lithium ionic cell positive material second particle that class is spherical, then itself and lithium source are sufficiently mixed and high temperature sintering system
Must have the ball-shaped lithium-ion battery anode material of nanoscale two-phase coexistent structure.The inventive method can effectively prevent MnO2Receive
Rice grain or coprecipitated product nanometer primary particle are individually reunited, it is thus achieved that the common reunion secondary of two kinds of even particle distribution
Grain product.The inventive method is simple to operate simultaneously, it is simple to large-scale production application, the anode material for lithium-ion batteries obtained
There is high specific capacity, good cyclical stability and wide charging/discharging voltage window.
The present invention is relative to the advantage of prior art:
1. the inventive method can effectively control in course of reaction coprecipitation process and oxidoreduction building-up process with
Step is carried out, and controls the MnO that redox reaction produces2The M (OH) that the coprecipitation reaction of nano-particle and transition metal produces2Receive
Rice grain is the most mutually reunited, and then just forms spherical or that class the is spherical lithium ion battery with nanoscale two-phase coexistent structure
Pole material precursor second particle.
2. the inventive method can control to synthesize any Mn4+/Mn3+The nanoscale two-phase coexistent that has of ratio and content is tied
The anode material for lithium-ion batteries of structure.Mn in product can be effectively controlled by the ratio controlling potassium permanganate and manganous salt4+
With Mn3+Ratio, can effectively control manganese element at product lithium by controlling the charge proportion of manganese element and other transition metal
Content in ion battery positive electrode.By Mn in regulation and control product4+/Mn3+Ratio and content can obtain and meet 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 inventive method synthesis, wherein Mn4+
With nanoscale Li2MnO3Form individually become and exist mutually, Li2MnO3Existence 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 below 4.5V
Li2MnO3Material is not involved in any electrochemical reaction, it is possible to plays skeletal support effect, effective stabilizing material structure, promotes material
Cycle performance.When charge cutoff voltage is higher than 4.5V, Li2MnO3Start progressively activate and discharge chemical property, significantly
Promote the volumetric properties of material.25 DEG C, when 3～4.5V, capacity boost 5～20mAh/g.
4. the inventive method is simple and easy to do, and the synthesis of material is by relatively simple coprecipitation reaction and redox reaction
Work in coordination with and carry out, it is possible to fully simplify production technology, reduce energy consumption, it is simple to continuous print industrialized production,
Accompanying drawing explanation
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 the anode material for lithium-ion batteries in embodiment 1 after sintering.
Fig. 3 is the anode material for lithium-ion batteries XRD figure in embodiment 1 after sintering.
Fig. 4 is the anode material for lithium-ion batteries 3-4.3V first charge-discharge curve chart in embodiment 1 after sintering.
Fig. 5 is the anode material for lithium-ion batteries 3-4.3V cycle performance curve chart in embodiment 1 after sintering.
Fig. 6 is the anode material for lithium-ion batteries 3-4.5V first charge-discharge curve chart in embodiment 1 after sintering.
Fig. 7 is the anode material for lithium-ion batteries 3-4.5V cycle performance curve chart in embodiment 1 after sintering.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes between each detailed description of the invention
Combination in any.
Detailed description of the invention one: present embodiment the ball-shaped lithium-ion battery with nanoscale two-phase coexistent structure just
Pole material is made up of two phase material, described biphase in a phase be Li2MnO3Phase, another phase is stratiform LiMO2Phase, M is Ni, Co,
The combination of one or more in Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo metal.
Detailed description of the invention two: the spherical lithium with nanoscale two-phase coexistent structure as described in detailed description of the invention one from
The method of sub-cell positive material sequentially includes the following steps:
One, the configuration of solution: be respectively configured potassium permanganate solution a that concentration is 0.01mol/L～2mol/L,
Complexing agent aqueous solution c, 0.01mol/L of precipitant aqueous solution b, 0.02mol/L～15mol/L of 0.01mol/L～5mol/L
～the hybrid metal saline solution d of 4mol/L and concentration are 0.01mol/L～4mol/L manganous salt aqueous solution e；
Two, react end liquid preparation: complexing agent aqueous solution c deionized water is diluted to concentration be 0.01mol/L～
The aqueous solution f of 5mol/L, and aqueous solution f is added in continuously stirred Liquid-phase reactor as liquid at the bottom of initial reaction；
Three, the preparation of presoma: control reaction temperature 35 DEG C～85 DEG C and the pH value 6.5～12 of reaction system, will mixing
Aqueous metal salt d, precipitant 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 simultaneously in the Liquid-phase reactor of continuous stirring, the most under stirring by potassium permanganate solution a and bivalent manganese saline
Solution e is with 1:(0.01～100) mol ratio add continuous stirring Liquid-phase reactor in, the rotating speed of described Liquid-phase reactor is
300r/min～1000r/min；Course of reaction keeps reactant liquor constant total volume；Reaction is down to room temperature, then after terminating naturally
Product is filtered and dries after 3 times～5 deionized water wash, dries temperature≤200 DEG C, obtain lithium ion battery
Positive electrode material precursor；
Four, high temperature process heat: by the precursor of lithium ionic cell positive material that obtains with lithium source by 1:(1～1.3)
Mixed in molar ratio also stirs 10～60 minutes and obtains solid mixture；It is then transferred in saggar compacting, in atmosphere sintering
In stove, at temperature 450 DEG C～700 DEG C, be incubated 3～10h, then proceed to be warming up to 700 DEG C～1000 DEG C and at 700 DEG C～
Carry out high temperature sintering 5～30h at 1000 DEG C, make lithium source fully react with persursor material；Reaction is down to room temperature after terminating and breaks
Broken, sieve, finally give and there is stratiform LiMO2And Li2MnO3The ball-shaped lithium-ion battery of the nanoscale two-phase coexistent structure of granule
Positive electrode.
Detailed description of the invention three: present embodiment unlike detailed description of the invention two, course of reaction described in step 3
Reactant liquor constant total volume is kept to be realized by the intermittent overflow of timing or seriality overflow；Described timing intermittence overflow
Concrete operation method is for often carrying out 1h～10h when reaction, and stopped reaction feeds, and after the sedimentation of question response product solid, opens overflow
Valve releases the supernatant, and the supernatant liquid measure every time released is consistent with the liquid inlet volume in this period, in the supernatant that overflow goes out
Do not contain product；How many regulation overflows being reacted into amount of liquid according to described seriality overflow concrete operation method go out
Amount of liquid so that in reactor total amount of liquid keep constant, the supernatant that overflow goes out includes product.Other steps
Identical with detailed description of the invention two with parameter.
Detailed description of the invention four: present embodiment, unlike detailed description of the invention two, in step 3 course of reaction is
Prevent MnO2The skewness phenomenon caused of individually reuniting of nano-particle, introduces excusing from death wave producer auxiliary in reaction system
Help dispersion.Other steps are identical with detailed description of the invention two with parameter.
Detailed description of the invention five: present embodiment unlike detailed description of the invention two, described mixed salt solution
For the combination of one or more in slaine hydrochlorate, metal nitrate, metal sulfate, metal acetate salt；Described mixing gold
The metal belonging to saline solution is the combination of one or more in Ni, Co, Mn, Al, Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo.Its
His step is identical with detailed description of the invention two with parameter.
Detailed description of the invention six: present embodiment is unlike detailed description of the invention two, in described complexing agent aqueous solution
Chelating agent be ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride,
A kind of or the most several combination in tartaric acid, maleic acid, succinic acid, citric acid, malonic acid.Other steps and parameter and tool
Body embodiment two is identical.
Detailed description of the invention seven: present embodiment is unlike detailed description of the invention two, in described precipitant aqueous solution
Precipitant be the one in ammonia, sodium hydroxide, potassium hydroxide, Lithium hydrate, sodium carbonate, potassium carbonate, lithium carbonate or wherein
Several combinations.Other steps are identical with detailed description of the invention two with parameter.
Detailed description of the invention eight: present embodiment unlike detailed description of the invention two, described lithium source be Lithium hydrate,
In lithium carbonate, lithium nitrate, lithium acetate Lithium hydrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate
The mixture of one or more.Other steps are identical with detailed description of the invention two with parameter.
Detailed description of the invention nine: present embodiment unlike detailed description of the invention two, atmosphere sintering described in step 4
Atmosphere in stove is O2Or air.Other steps are identical with detailed description of the invention two with parameter.
Embodiment one
First, nickel sulfate and the cobaltous sulfate hybrid metal that mol ratio is Ni:Co=8:1 and total concentration is 2.0mol/L is prepared
Saline solution, the chelating agent ammonia spirit of 3.0mol/L, the precipitant sodium hydroxide solution of 2.0mol/L, the ammonia of 0.5mol/L is molten
Liquid, the KMnO of 2mol/L4Solution, the manganese sulfate solution of 2.0mol/L.
Take the chelating agent ammonia spirit of 3.0mol/L and be diluted to the ammonia spirit of 0.5mol/L as reaction end liquid, then will
It joins in reactor.
At inert N2Under atmosphere protection, will reaction end liquid heat to 50 DEG C, then by molten to mixed salt solution, ammonia
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 reactor, make KMnO simultaneously4Solution and manganese sulfate solution fully react generation nanometer MnO2Granule and with co-precipitation
Product is reunited altogether.Control the pH of whole reaction system 11, and carry out primary overflow every 1h and keep reactant liquor to be volume 1.5L,
Coreaction 15 hours.
After after having reacted, clean 5 times the soluble impurity removed in material with deionized water, then filter, in vacuum
Under the conditions of 120 DEG C dry materials, obtain precursor of lithium ionic cell positive material powder.
Weigh precursor of lithium ionic cell positive material powder 25g, a hydronium(ion) lithium oxide 12.0g, be 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 is incubated 5h at 500 DEG C, then heat to 800 DEG C and be incubated at 800 DEG C
15h, makes Lithium hydrate fully react with persursor material, obtains the lithium ion with nanoscale two-phase coexistent structure that class is spherical
Cell positive material 0.1Li2MnO3·0.9LiNi0.8Co0.1O2。
Test result shows: as shown in the scanning electron microscope (SEM) photograph (SEM) of persursor material in Fig. 1, and persursor material is once
Grain is in flaky nanometer structure, and second particle is that class is spherical, and average-size is 7.2 μm；Lithium ion cell positive after sintering in Fig. 2
Shown in scanning electron microscope (SEM) figure of material, after sintering, material primary particle is that nanometer is block, and it is spherical that second particle is still class；
Being tested can be drawn by the XRD of Fig. 3, the material after sintering in the present embodiment has good Lamellar character, and free from admixture phase
Exist；By first charge-discharge curve in Fig. 4 it can be seen that 25 DEG C, during 3V～4.3V, first charge-discharge circulation coulombic efficiency
88.8%, first discharge specific capacity is 203.8mAh/g；By cycle performance test curve in Fig. 5 it can be seen that 1C (200mA/g)
Under under multiplying power, capacity is 178.4mAh/g, 1C (200mA/g) multiplying power, 100 circulation volume conservation rates are 96.2%.By Fig. 6 and Fig. 7
Middle first charge-discharge curve and cycle performance curve are it can be seen that 25 DEG C, during 3V～4.5V, and first charge-discharge circulation coulombic efficiency
86.9%, first discharge specific capacity is that under 218.5mAh/g, 1C (200mA/g) multiplying power, capacity is 200.9mAh/g, 1C (200mA/
G) under multiplying power, 100 circulation volume conservation rates are 74.2%.
Claims (9)
1. a ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure: it is characterized in that: this material by
Two phase material form, described biphase in a phase be Li2MnO3Phase, another phase is stratiform LiMO2Phase, M is Ni, Co, Mn, Al,
The combination of one or more in Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo metal.
A kind of side of the ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure
Method: it is characterized in that: the method sequentially includes the following steps:
One, the configuration of solution: be respectively configured potassium permanganate solution a, 0.01mol/L that concentration is 0.01mol/L～2mol/L
～complexing agent aqueous solution c, 0.01mol/L～4mol/L of precipitant aqueous solution b, 0.02mol/L～15mol/L of 5mol/L
Hybrid metal saline solution d and concentration are 0.01mol/L～4mol/L manganous salt aqueous solution e；
Two, the preparation of end liquid is reacted: complexing agent aqueous solution c deionized water is diluted to concentration is 0.01mol/L～5mol/L
Aqueous solution f, and aqueous solution f is added in continuously stirred Liquid-phase reactor as liquid at the bottom of initial reaction；
Three, the preparation of presoma: control reaction temperature 35 DEG C～85 DEG C and the pH value 6.5～12 of reaction system, by hybrid metal
Saline solution d, precipitant aqueous solution b and complexing agent aqueous solution c are with 1:(0.1～10): the feed rate of (0.1～10) is than simultaneously
Inject in the Liquid-phase reactor of continuous stirring, the most under stirring by potassium permanganate solution a and manganous salt aqueous solution e
With 1:(0.01～100) mol ratio add continuous stirring Liquid-phase reactor in, the rotating speed of described Liquid-phase reactor is 300r/
Min～1000r/min；Course of reaction keeps reactant liquor constant total volume；Room temperature is down in reaction naturally after terminating, then will reaction
Product filters and dries after 3 times～5 deionized water wash, dries temperature≤200 DEG C, obtains lithium ion cell positive material
Material precursor；
Four, high temperature process heat: by the precursor of lithium ionic cell positive material that obtains with lithium source by 1:(1～1.3) mole
Ratio is mixed and stirred for 10～60 minutes obtaining solid mixture；It is then transferred in saggar compacting, in atmosphere sintering furnace,
At temperature 450 DEG C～700 DEG C, it is incubated 3～10h, then proceedes to be warming up to 700 DEG C～1000 DEG C and at 700 DEG C～1000 DEG C
Carry out high temperature sintering 5～30h, make lithium source fully react with persursor material；Reaction is down to room temperature after terminating and crushes, sieves,
Finally give and there is stratiform LiMO2And Li2MnO3The ball-shaped lithium-ion battery anode material of the nanoscale two-phase coexistent structure of granule
Material.
The ball-shaped lithium-ion with nanoscale two-phase coexistent structure of a kind of Co deposited synthesis the most according to claim 2
The method of cell positive material: it is characterized in that: course of reaction described in step 3 keeps reactant liquor constant total volume to be by fixed
Time intermittence overflow or seriality overflow realize；Described timing intermittence overflow concrete operation method is for often carrying out 1h when reaction
～10h, stopped reaction feeds, and after the sedimentation of question response product solid, opens flow spill valve and releases the supernatant, and that releases is upper every time
Clear liquid amount is consistent with the liquid inlet volume in this period, does not contains product in the supernatant that overflow goes out；Described seriality overflow
The amount of liquid how many regulation overflows of amount of liquid go out it is reacted into so that total amount of liquid in reactor according to concrete operation method
Keep constant, the supernatant that overflow goes out includes product.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: for preventing MnO in step 3 course of reaction2The skewness caused of individually reuniting of nano-particle
Phenomenon, introduces excusing from death wave producer aid dispersion in reaction system.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: the slaine in described hybrid metal saline solution is slaine hydrochlorate, metal nitrate, metal sulfur
The combination of one or more in hydrochlorate, metal acetate salt；The metal of described hybrid metal saline solution is Ni, Co, Mn, Al,
The combination of one or more in Mg, Zn, Cr, V, Zr, Fe, Ti, Cu, Mo.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: the chelating agent in described complexing agent aqueous solution be ammonia, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate,
One in EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, malonic acid or
The most several combinations.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: the precipitant in described precipitant aqueous solution be ammonia, sodium hydroxide, potassium hydroxide, Lithium hydrate,
A kind of or the most several combination in sodium carbonate, potassium carbonate, lithium carbonate.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: described lithium source is Lithium hydrate, lithium carbonate, lithium nitrate, lithium acetate Lithium hydrate, lithium sulfate, chlorination
The mixture of one or more in lithium, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate.
A kind of ball-shaped lithium-ion battery anode material with nanoscale two-phase coexistent structure the most according to claim 2
Method: it is characterized in that: the atmosphere in atmosphere sintering furnace described in step 4 is O2Or air.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816601A (en) * | 2017-01-14 | 2017-06-09 | 复旦大学 | Lithium-rich manganese-based anode material and its preparation method and application |
| CN107293742A (en) * | 2017-07-25 | 2017-10-24 | 黄冈林立新能源科技有限公司 | A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology |
| CN109950533A (en) * | 2019-03-01 | 2019-06-28 | 珠海光宇电池有限公司 | A kind of positive electrode and preparation method thereof |
| CN112701262A (en) * | 2020-12-29 | 2021-04-23 | 浙江工业大学 | Inert Li2MnO3Phase-doped layered lithium manganate material and preparation and application thereof |
| US11522182B2 (en) | 2017-09-26 | 2022-12-06 | Lg Energy Solution, Ltd. | Method for producing lithium manganese oxide-based cathode active material |
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| CN1336016A (en) * | 1999-10-08 | 2002-02-13 | 全球热电公司 | Composite electrodes for solid state electrochemical devices |
| CN102169979A (en) * | 2010-02-26 | 2011-08-31 | 比亚迪股份有限公司 | Activating method of cathode material |
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Patent Citations (2)
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| CN1336016A (en) * | 1999-10-08 | 2002-02-13 | 全球热电公司 | Composite electrodes for solid state electrochemical devices |
| CN102169979A (en) * | 2010-02-26 | 2011-08-31 | 比亚迪股份有限公司 | Activating method of cathode material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106816601A (en) * | 2017-01-14 | 2017-06-09 | 复旦大学 | Lithium-rich manganese-based anode material and its preparation method and application |
| CN106816601B (en) * | 2017-01-14 | 2020-07-28 | 复旦大学 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN107293742A (en) * | 2017-07-25 | 2017-10-24 | 黄冈林立新能源科技有限公司 | A kind of preparation method of the electric positive electrode of the lithium of stratiform monoclinic phase-Spinel integrated morphology |
| US11522182B2 (en) | 2017-09-26 | 2022-12-06 | Lg Energy Solution, Ltd. | Method for producing lithium manganese oxide-based cathode active material |
| CN109950533A (en) * | 2019-03-01 | 2019-06-28 | 珠海光宇电池有限公司 | A kind of positive electrode and preparation method thereof |
| CN109950533B (en) * | 2019-03-01 | 2021-06-29 | 珠海冠宇电池股份有限公司 | Positive electrode material and preparation method thereof |
| CN112701262A (en) * | 2020-12-29 | 2021-04-23 | 浙江工业大学 | Inert Li2MnO3Phase-doped layered lithium manganate material and preparation and application thereof |
| CN112701262B (en) * | 2020-12-29 | 2022-07-22 | 浙江工业大学 | Inert Li2MnO3Phase-doped layered lithium manganate material and preparation and application thereof |
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