CN103258994B - Positive material for lithium ion battery, preparation method of material, and lithium ion battery - Google Patents
Positive material for lithium ion battery, preparation method of material, and lithium ion battery Download PDFInfo
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- CN103258994B CN103258994B CN201310162372.XA CN201310162372A CN103258994B CN 103258994 B CN103258994 B CN 103258994B CN 201310162372 A CN201310162372 A CN 201310162372A CN 103258994 B CN103258994 B CN 103258994B
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Abstract
The invention provides a positive material for a lithium ion battery and a preparation method thereof. The method comprises the following steps of: providing nano lithium phosphate with a hollow structure; mixing the nano lithium phosphate, a soluble manganese source compound and an additive with a mixed solvent of water and polyhydric alcohol; carrying out ball milling to obtain a mixed solution; then keeping heat of the mixed solution in a closed reaction kettle filled with inert gas under the condition that the temperature is 150-230 DEG C to obtain lithium phosphate; mixing the lithium phosphate with a carbon source compound and carrying out the ball milling; and calcining to obtain the positive material for the lithium ion battery of carbon coated lithium phosphate. According to the positive material and the preparation method thereof disclosed by the invention, polyhydric alcohol-hydrothermal reaction between a solid and liquid can be carried out on the lithium phosphate and the soluble manganese source compound, so that the grain diameter of a lithium phosphate crystal is effectively reduced and a crystal form of the lithium phosphate crystal is integrally formed; and furthermore, the positive material for the lithium ion battery with high specific capacity and specific energy can be obtained and is good for popularization. The invention further provides the lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly anode material for lithium-ion batteries, its preparation method and lithium ion battery.
Background technology
Continually developing of new forms of energy is the important foundation of human social.Along with the progress of science and technology, people, to the demand of the removable energy, particularly constantly strengthen with the aggravation of oil and environmental crisis the demand of pure electric vehicle.But inexpensive, safety, environmental friendliness, excellent performance secondary chemical sources of electric energy technology has become the bottleneck of the pure electric vehicle development of restriction at present.In the lithium ion battery material positive electrode that can be used as secondary chemical sources of electric energy application, although the cobalt acid lithium (LiCoO of stratiform
2), lithium nickelate (LiNiO
2) obtain business use, but, the resource scarcity of cobalt, expensive and cause lithium ion battery production cost higher, and cobalt acid lithium and the chemical/electrochemical stability of lithium nickelate when high oxidation state very poor, thus the scope of application of cobalt acid lithium and lithium nickelate to be limited to some extent.In addition, there is the LiMn2O4 (LiMn of spinel structure
2o
4) can dissolve in the electrolytic solution when high-temperature storage and cause the significantly decay of capacity.Therefore, above-mentioned material all can not meet the requirement of electrokinetic cell.
Since A.K.Padhi etc. found the LiFePO with olivine structural in 1997
4can since reversible discharge and recharge, olivine-type material LiFePO
4, LiMnPO
4, LiCoPO
4and LiNiPO
4extensive concern is received as anode material for lithium-ion batteries.Wherein, due to LiFePO
4theoretical capacity up to 170mAhg
-1, it has started to commercially produce, and is successfully applied to electric vehicle.But, Fe
3+/ Fe
2+relative to Li
+the electrode potential of/Li is only 3.4V, and this limits LiFePO to a certain extent
4the development of material.And for having same high theoretical capacity (170mAhg
-1) LiMnPO
4material, Mn
3+/ Mn
2+relative to Li
+the electrode potential of/Li is up to 4.1V, and it has electrolyte and stablizes, do not decompose and make this material have the advantage of potential high-energy-density under this high potential.In addition, manganese is abundanter in china natural resources, LiMnPO
4the cost of synthesis is low, environmentally friendly.Therefore, LiMnPO
4research and development to the development of the national economy of China and the utilization of promoter manganese, there is positive effect.
At present, LiMnPO is synthesized
4method mainly contain high temperature solid-state method, liquid-phase coprecipitation, sol-gal process, polyol process, hydro thermal method, hydrolysis methods and mechanochemical reaction.Wherein, high temperature solid-state method is the most common, also relative the most applicable industrialized production process.Such as, domestic Wang Zhi is emerging waits people (China YouSe Acta Metallurgica Sinica, 2008(4): 660-665) by composition LiMnPO
4stoichiometric proportion, take Li
2cO
3, MnCO
3and NH
4h
2pO
4, and mix with appropriate carbon black, carbon theoretical content is in the product that 10%(quality is than mark), then mixture is carried out ball milling, at N
2in 300 DEG C of pre-burning 3h under atmosphere, obtain intermediate product, then after being taken out and carrying out second time ball milling, at N
2sinter in uniform temperature under atmosphere, be after this cooled to room temperature, obtain end product.But, the LiMnPO that the method synthesizes
4chemical property still have much room for improvement.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery, preparation method provided by the invention can synthesize the manganese-lithium phosphate anode material that specific capacity is high and capability retention is high.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
A) provide nanometer lithium phosphate, described nanometer lithium phosphate has hollow-core construction;
B) ball milling is carried out after the mixed solvent that the nanometer lithium phosphate described step a) provided, soluble manganese source compound, additive and water and polyalcohol form mixes, obtain mixed solution, then by described mixed solution logical inert gas close reactor in, be be incubated under the condition of 150 DEG C ~ 230 DEG C in temperature, obtain lithium manganese phosphate;
C) carry out ball milling after being mixed with carbon-source cpd by the lithium manganese phosphate that described step b) obtains, through calcining, obtain the anode material for lithium-ion batteries of the coated lithium manganese phosphate of carbon.
Preferably, in described step a), described nanometer lithium phosphate is prepared in accordance with the following methods:
Li source compound solution is provided, then under agitation adds P source compound solution wherein and react, continue after reaction to stir, after filtration, obtain the nanometer lithium phosphate with hollow-core construction.
Preferably, in described step a), when continuing after reaction to stir, the speed of described stirring is 300rpm ~ 800rpm, and the time is 0.5h ~ 3h.
Preferably, in described step b), in the mixed solvent that water and polyalcohol form, the mol ratio of described water and polyalcohol is greater than 0 and is less than or equal to 400.
Preferably, in described step b), described polyalcohol is selected from one or more in diethylene glycol, BDO, ethylene glycol, 1,2-PD, neopentyl glycol, dipropylene glycol, glycerine, pentaerythrite and trimethylolethane.
Preferably, in described step b), described additive is selected from one or more in citric acid, ascorbic acid, malic acid, lactic acid, oxalic acid and tartaric acid.
Preferably, in described step b), the time of described ball milling is 0.5h ~ 15h.
Preferably, in described step b), the time of described insulation is 7h ~ 36h.
The invention provides a kind of anode material for lithium-ion batteries, wherein, preparation method by mentioned earlier obtains.
The present invention also provides a kind of lithium ion battery, comprises positive pole, negative pole and electrolyte, and wherein, described positive pole comprises anode material for lithium-ion batteries mentioned above.
Compared with prior art, first the present invention provides the nanometer lithium phosphate with hollow-core construction; Then, mix the mixed solvent that described nanometer lithium phosphate, soluble manganese source compound, additive and water and polyalcohol form, through ball milling, obtain mixed solution, be placed on logical inert gas close reactor in 150 DEG C ~ 230 DEG C insulations, obtain lithium manganese phosphate; Finally described lithium manganese phosphate is mixed with carbon-source cpd, through ball milling and calcining, obtain the anode material for lithium-ion batteries of the coated lithium manganese phosphate of carbon.Nanometer lithium phosphate provided by the invention is hollow-core construction, in the process of synthesis lithium manganese phosphate, lithium manganese phosphate can preferentially at the Surface Creation of lithium phosphate, due to the acting in conjunction of the unsteadiness of hollow-core construction and the lithium manganese phosphate solubility product these two aspects larger relative to LiFePO4 itself, this structure is very easily cracked, thus can obtain more tiny lithium manganese phosphate crystal.On this basis, polyalcohol-hydro-thermal reaction that the present invention adopts described lithium phosphate and soluble manganese source compound to carry out between solid-liquid, can effectively reduce the particle diameter of lithium manganese phosphate crystal, and it is complete that the crystal formation of lithium manganese phosphate crystal is generated.Wherein, the polyalcohol that the present invention introduces both can be used as solvent and had participated in reaction, the growth course of controlled combinations body again.Therefore, by changing the size of the mol ratio of water and polyalcohol, the regulation and control of pattern to product phosphoric acid manganese crystalline lithium and particle diameter can be realized, and then the anode material for lithium-ion batteries with height ratio capacity and specific energy can be obtained.Accordingly, described anode material for lithium-ion batteries can improve the performance of lithium ion battery, is beneficial to application.
In addition, the polyol solvent that the present invention adopts reclaims by rectifying, realizes recycling, low-carbon environment-friendly.Further, preparation method's technique of the present invention is simple, with low cost.
Further, the present invention adopts the organic acid with reproducibility as reaction promoter, can suppress the oxidation of divalent manganesetion, effectively avoid the generation of dephasign while providing sour environment for reaction system.Further, at the initial stage that lithium manganese phosphate generates, described organic acid effectively can reduce the reunion degree of lithium manganese phosphate at the surface of solids by the absorption that hydrogen bond occurs, and is beneficial to and obtains the higher anode material for lithium-ion batteries of chemical property.
Accompanying drawing explanation
Fig. 1 is the Li that the embodiment of the present invention 1 obtains
3pO
4sEM image under 30.0k;
Fig. 2 is the Li that the embodiment of the present invention 1 obtains
3pO
4sEM image under 100k;
Fig. 3 is LiMnPO prepared by the embodiment of the present invention 1
4the X-ray diffraction contrast collection of illustrative plates of/C positive electrode material;
Fig. 4 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4
4the charging and discharging curve of/C positive electrode material;
Fig. 5 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4
4the cycle performance curve of/C positive electrode material;
Fig. 6 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4
4the X-ray diffracting spectrum of/C positive electrode material.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
A) provide nanometer lithium phosphate, described nanometer lithium phosphate has hollow-core construction;
B) ball milling is carried out after the mixed solvent that the nanometer lithium phosphate described step a) provided, soluble manganese source compound, additive and water and polyalcohol form mixes, obtain mixed solution, then by described mixed solution logical inert gas close reactor in, be be incubated under the condition of 150 DEG C ~ 230 DEG C in temperature, obtain lithium manganese phosphate;
C) carry out ball milling after being mixed with carbon-source cpd by the lithium manganese phosphate that described step b) obtains, through calcining, obtain the anode material for lithium-ion batteries of the coated lithium manganese phosphate of carbon.
The preparation method of lithium ion battery anode material manganese lithium phosphate provided by the invention is polyalcohol-hydrothermal synthesis method, is a kind of new synthetic method, mainly solves the problem of the low and cycle performance difference of actual capacity that existing lithium manganese phosphate material exists.
First the embodiment of the present invention provides the nanometer lithium phosphate with hollow-core construction, to carry out subsequent reactions.
In the present invention, described nanometer lithium phosphate is preferably prepared in accordance with the following methods:
Li source compound solution is provided, then under agitation adds P source compound solution wherein and react, continue after reaction to stir, after filtration, obtain the nanometer lithium phosphate with hollow-core construction.
Particularly, Li source compound solution adds in stirring reaction device by the embodiment of the present invention, then under agitation adds P source compound solution wherein and reacts, continue after reaction to stir, reaction generates sediment, after filtration, obtains the nanometer lithium phosphate with hollow-core construction.
The present invention adopts Li source compound and the P source compound of different mol ratio, as synthesis lithium phosphate (Li
3pO
4) presoma.Described Li source compound is preferably one or more in lithium hydroxide, lithium acetate, lithium carbonate, lithium sulfate, lithium oxalate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithium, lithium benzoate, lithium chloride, lithium nitrate, lithium fluoride, lithium bromide and lithium citrate, is more preferably lithium hydroxide (LiOHH
2o), lithium sulfate (Li
2sO
4) or lithium nitrate (LiNO
3).Described P source compound is water-soluble phosphorus-containing compound, be preferably one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium, be more preferably phosphoric acid (H
3pO
4) or lithium dihydrogen phosphate (LiH
2pO
4).The mol ratio of described Li source compound and P source compound is preferably (3 ~ 1): 1.
P source compound solution, subsequently under agitation, adds in described stirring reaction device with certain charging rate for end liquid first adds in stirring reaction device with Li source compound solution by the present invention.
The present invention directly can provide Li source compound solution and P source compound solution, also Li source compound and P source compound can be made into certain density solution respectively.The pH value of described Li source compound solution is preferably 10 ~ 14, and concentration can be 1.2molL
-1~ 2.5molL
-1.The present invention preferably with the rotating speed of 100rpm ~ 2500rpm, more preferably with the rotating speed of 500rpm ~ 1500rpm, most preferably with the rotating speed of 600rpm ~ 1000rpm, be stirred to described Li source compound solution pH value stablize.
Then, under agitation, the present invention adds P source compound solution preferably by peristaltic pump.When adding P source compound solution, charging rate can add for 0.1mL/min ~ disposable, is preferably 0.5mL/min ~ 0.9mL/min; The speed of described stirring is preferably 100rpm ~ 2500rpm, is more preferably 500rpm ~ 1500rpm, most preferably is 600rpm ~ 1000rpm.
After P source compound solution adds, reacts and terminate, continue to stir a period of time, then the precipitation that reaction generates carried out successively filter, wash, to filter and dry, obtain the Li of white
3pO
4powder.
After described P source compound solution adds end, the pH value of reaction system solution is preferably greater than or equal to 11.P source compound solution terminates, react after continue stir time, the speed of described stirring is preferably 300rpm ~ 800rpm, is more preferably 300rpm ~ 500rpm; The time of described stirring is preferably 0.5h ~ 3h, is more preferably 0.5h ~ 1.5h.Described filtration, washing, drying are technological means well known to those skilled in the art, and the present invention is not particularly limited, and wherein, described filtration can be suction filtration.
The Li of the white obtained
3pO
4powder is nanometer lithium phosphate, and is hollow ball structure.The particle diameter of described nanometer lithium phosphate is preferably 20nm ~ 800nm, is more preferably 50nm ~ 600nm.The present invention preferably adopts intermediate processing, the obtained nanometer lithium phosphate particle with hollow-core construction of success, and described in there is hollow-core construction nanometer lithium phosphate be realize a basis of the present invention, in the process of synthesis lithium manganese phosphate, lithium manganese phosphate can preferentially at the Surface Creation of lithium phosphate, due to the acting in conjunction of the unsteadiness of hollow-core construction and the lithium manganese phosphate solubility product these two aspects larger relative to LiFePO4 itself, this structure is very easily cracked, thus can obtain more tiny lithium manganese phosphate crystal.
On this basis, the mixed solvent that the nanometer lithium phosphate with hollow-core construction obtained, soluble manganese source compound, additive form with water and polyalcohol mixes by the embodiment of the present invention, then carries out ball milling, obtains mixed solution.
The present invention mainly adopts described nanometer lithium phosphate and soluble manganese source compound synthesis lithium manganese phosphate (LiMnPO
4), described soluble manganese source compound and solubility, containing manganese compound, are preferably one or more in manganese acetate, manganese sulfate, manganese nitrate, manganese chloride and manganese oxalate, are more preferably manganese sulfate (MnSO
4h
2o), manganese chloride (MnCl
2), manganese nitrate (Mn(NO
3)
2) or manganese oxalate (MnC
2o
4).The mol ratio of described nanometer lithium phosphate and soluble manganese source compound is preferably 1:1.
During mixing, the present invention preferably first adds described nanometer lithium phosphate and soluble manganese source compound, then adds a small amount of additive, then adds the mixed solvent of water and polyalcohol composition.
The present invention take additive as reaction promoter, and described additive is preferably organic acid, is more preferably one or more in citric acid, ascorbic acid, malic acid, lactic acid, oxalic acid and tartaric acid, most preferably is ascorbic acid.The consumption of described additive is relevant with the output of end product, is preferably end product and lithium manganese phosphate (LiMnPO
4) the 0.1%-20% of quality, be more preferably 1% ~ 10%.
The present invention preferably adopts the organic acid with reproducibility as reaction promoter, can suppress the oxidation of divalent manganesetion, effectively avoid the generation of dephasign while providing sour environment for reaction system.Further, at the initial stage that lithium manganese phosphate generates, described organic acid effectively can reduce the reunion degree of lithium manganese phosphate at the surface of solids by the absorption that hydrogen bond occurs, and is beneficial to and obtains the higher anode material for lithium-ion batteries of chemical property.
The present invention with water and polyalcohol composition mixed solvent for solvent or dispersant, described polyalcohol is preferably diethylene glycol, 1,4-butanediol, ethylene glycol, 1, one or more in 2-propylene glycol, neopentyl glycol, dipropylene glycol, glycerine, pentaerythrite and trimethylolethane, be more preferably diethylene glycol, BDO, glycerine or pentaerythrite.Wherein, diethylene glycol has another name called diethylene glycol (DEG), and glycerine has another name called glycerol, and the name that trimethylolethane is conventional is called 2-hydroxy methane-2-methyl isophthalic acid, 3 propylene glycol.In the present invention, described polyalcohol both can be used as solvent and had participated in reaction, and the growth course of controlled combinations body again, that is, described polyalcohol is reaction medium, is again the adjusting control agent of crystal growth.In addition, the polyol solvent that the present invention adopts reclaims by rectifying, realizes recycling, low-carbon environment-friendly.
The consumption of the present invention to the mixed solvent that described water and polyalcohol form is not particularly limited, and can realize the present invention.In the mixed solvent of water and polyalcohol composition, the mol ratio of described water and polyalcohol is preferably greater than 0 and is less than or equal to 400, is less than or equal to 300, is most preferably greater than 2 and is less than or equal to 200 more preferably greater than 1.The present invention, by changing the size of the mol ratio of water and polyalcohol, can realize the regulation and control of pattern to product phosphoric acid manganese crystalline lithium and particle diameter, and then can obtain the anode material for lithium-ion batteries with height ratio capacity and specific energy.
Above-mentioned material is placed in ball grinder and carries out ball milling by the present invention, after being uniformly dispersed, obtains mixed solution.Described ball grinder is the ball mill that this area is commonly used, and can adopt planetary ball mill, horizontal drum ball mill or stirring ball mill, is preferably polyurethane ball-milling pot.Described ball milling is preferably airtight liquid phase ball milling; The time of described ball milling is preferably 0.5h ~ 15h, is more preferably 0.5h ~ 10h, most preferably is 0.5h ~ 5h.
Then, the mixed solution that described ball milling obtains by the embodiment of the present invention is transferred to rapidly in reactor, is sealed by described reactor, be incubated under the condition of 150 DEG C ~ 230 DEG C, obtain lithium manganese phosphate in temperature after logical inert gas.
The present invention synthesizes lithium manganese phosphate under hydrothermal conditions, can effectively reduce the particle diameter of lithium manganese phosphate crystal, and it is complete that the crystal formation of lithium manganese phosphate crystal is generated.During synthesis, the temperature of insulation is 150 DEG C ~ 230 DEG C, is preferably 170 DEG C ~ 220 DEG C; The time of described insulation is preferably 7h ~ 36h, more preferably 8h ~ 30h, most preferably is 10h ~ 20h.The present invention is logical inert gas 5min preferably, and sealed by reactor, described inert gas is preferably one or more in argon gas, helium and nitrogen, is more preferably argon gas (Ar).Described reactor is the hydrothermal reaction kettle that this area is commonly used, and the present invention is not particularly limited.
After completing synthesis, be cooled to room temperature, the precipitation in still is carried out filtering, washs, is filtered by the present invention successively, and at 80 DEG C ~ 120 DEG C vacuum drying, obtain linen product LiMnPO
4.Described filtration, washing are technological means well known to those skilled in the art, and the present invention is not particularly limited, and wherein, described filtration can be suction filtration.
After obtaining described lithium manganese phosphate, it mixes with a certain amount of carbon-source cpd by the embodiment of the present invention, ball milling in ball mill, through calcining, obtains the coated lithium manganese phosphate (LiMnPO of carbon
4/ C) anode material for lithium-ion batteries.
The present invention adopts carbon-source cpd to carry out the coated process of carbon, to be applied in lithium ion battery to described lithium manganese phosphate.Described carbon-source cpd is preferably carbonaceous organic material, is more preferably one or more in sucrose, glucose, fructose, lactose, citric acid, ascorbic acid, carboxymethyl cellulose and phenolic resins, most preferably is sucrose, citric acid or ascorbic acid.
After mixing, the present invention is ball milling in ball mill, calcines, obtain LiMnPO evenly
4/ C positive electrode material.Described ball mill is the ball grinder that this area is commonly used, and can adopt planetary ball mill, horizontal drum ball mill or stirring ball mill.The time of described ball milling is preferably 1h ~ 5h, is more preferably 3h ~ 5h.
The temperature of described calcining is preferably 500 DEG C ~ 750 DEG C, is more preferably 550 DEG C ~ 700 DEG C; Time is preferably 3h ~ 10h, is more preferably 5h ~ 10h.Described calcining is preferably carried out under inert gas atmosphere, and described inert gas is preferably one or more in argon gas, helium and nitrogen, is more preferably argon gas (Ar).The equipment of described calcining can be tube furnace, box type furnace, rotary furnace or continuous tunnel furnace, and the present invention is not particularly limited.
At LiMnPO
4in/C positive electrode material, the content of described coated carbon is preferably LiMnPO
41% ~ 13%(mass percent of/C), be more preferably LiMnPO
42% ~ 10%(mass percent of/C).
After obtaining described anode material for lithium-ion batteries, the present invention is carried out X-ray diffraction (XRD) test.Test result shows, described anode material for lithium-ion batteries is lithium manganese phosphate, and purity is high, and thing is mutually single, and crystal formation integrality is better.
Accordingly, the invention provides a kind of anode material for lithium-ion batteries, its preparation method by mentioned earlier obtains, and its crystal formation generates complete, and particle is tiny.
The present invention carries out charge and discharge cycles test after described anode material for lithium-ion batteries is made button cell, test result shows, this material has obvious discharge platform at about 4V, when 0.05C rate charge-discharge, specific discharge capacity is up to 162mAh/g, further, this material has good cycle performance.
In addition, the preparation method of anode material for lithium-ion batteries provided by the invention is a kind of new glass forming theory of manganese-lithium phosphate anode material, and technique is simple, controlled, with low cost, is easy to apply.
Present invention also offers a kind of lithium ion battery, comprise positive pole, negative pole and electrolyte, wherein, described positive pole comprises anode material for lithium-ion batteries mentioned above.
The present invention adopts above-mentioned anode material for lithium-ion batteries, makes positive pole after mixing with conductive agent and binding agent.The present invention is not particularly limited the method making positive pole, and wherein, described conductive agent can be acetylene black, and described binding agent can be Kynoar (PVDF), described LiMnPO
4the mass ratio of/C positive electrode material, conductive agent acetylene black and binding agent PVDF is preferably 80:10:10.The present invention can add appropriate 1-METHYLPYRROLIDONE (NMP) in described mixture, be coated on aluminium foil that thickness is 0.17mm after stirring, vacuumize 10h at 80 DEG C, compacting again after cut-parts, then vacuum drying 10h at 120 DEG C, then the disk and positive plate that are washed into that diameter is 1.3cm.
The present invention is not particularly limited described negative pole, electrolyte etc., can take metal lithium sheet as negative pole, with Celgard2325 microporous polypropylene membrane for barrier film, with LB315 lithium battery electrolytes for electrolyte, in LB315 lithium battery electrolytes, dimethyl carbonate (DMC), diethyl carbonate (DEC) are 1:1:1 with the mass ratio of ethylene carbonate (EC).Described positive pole, negative pole and barrier film etc. are assembled into fastening lithium ionic cell by the present invention in the glove box being full of argon gas.
Above-mentioned anode material for lithium-ion batteries crystal formation generates complete, and particle is tiny, has nanostructure, height ratio capacity and specific energy, and therefore, it can make the performance of described lithium ion battery be improved, and is beneficial to application.
In order to understand the present invention further, below in conjunction with embodiment, anode material for lithium-ion batteries provided by the invention, its preparation method and lithium ion battery are specifically described.
Embodiment 1
Be 2.5molL by concentration
-1liOHH
2o solution adds in stirring reaction device, is stirred to pH stablizes with the rotating speed of 600rpm, is then 1.1molL by peristaltic pump by concentration
-1phosphoric acid (H
3pO
4) solution adds in described stirring reaction device with the charging rate of 0.8mL/min and react, wherein, LiOHH
2o and H
3pO
4mol ratio be 3:1, after phosphoric acid solution adds, then stir 30min with the speed of 300rpm, reaction generates sediment, is carried out by described sediment washing, suction filtration and drying, obtains the Li of white
3pO
4powder.
By the Li obtained
3pO
4powder carries out sem analysis, and result is the Li that the embodiment of the present invention 1 obtains see Fig. 1 and Fig. 2, Fig. 1
3pO
4sEM image under 30.0k, Fig. 2 is the Li that the embodiment of the present invention 1 obtains
3pO
4sEM image under 100k.From Fig. 1 and Fig. 2, gained Li
3pO
4particle diameter at about 500nm, and be hollow ball structure.
Be 1:1 according to mol ratio, by described Li
3pO
4powder and MnSO
4h
2o is transferred to polyurethane ball-milling pot, add 0.45g ascorbic acid, add the mixed solvent that 60mL water and diethylene glycol (DEG) form again, wherein, the mol ratio of described water and diethylene glycol (DEG) is 200, carry out liquid phase ball milling 0.5h, obtain mixed solution, then described mixed solution is transferred to rapidly in the hydrothermal reaction kettle of 100mL, logical 5min argon gas (Ar), described hydrothermal reaction kettle is sealed, be be incubated under the condition of 150 DEG C in temperature, room temperature is cooled to after 10h, finally the precipitation in still is washed, suction filtration, and at 80 DEG C vacuum drying, obtain linen product LiMnPO
4.
Take LiMnPO described in 15g
4be placed in ball grinder with 1.5g sucrose, ball milling 5h, then in 600 DEG C, calcine under argon gas atmosphere, obtain the coated lithium manganese phosphate (LiMnPO of carbon after 10h
4/ C) positive electrode.
By the LiMnPO obtained
4the standard card of/C positive electrode material and JCPDS#74-0725(lithium manganese phosphate) to carry out X-ray diffraction and contrast and test, as shown in Figure 3, Fig. 3 is LiMnPO prepared by the embodiment of the present invention 1 to test result
4the X-ray diffracting spectrum of/C positive electrode material.The abscissa of Fig. 3 is angular dimension, indicates peak position, and ordinate is intensity, represents perfection of crystal, and intensity is larger, and crystal growth must be better.As can be seen from Figure 3, gained LiMnPO
4/ C positive electrode material and JCPDS#74-0725 fit like a glove, and show that it is lithium manganese phosphate, and purity is high, thing is mutually single.
By described LiMnPO
4/ C positive electrode material, conductive agent acetylene black and binding agent PVDF in mass ratio 80:10:10 weigh and mix, add appropriate NMP, be coated on aluminium foil that thickness is 0.17mm after stirring, vacuumize 10h at 80 DEG C, compacting again after cut-parts, then vacuum drying 10h at 120 DEG C, then the disk and positive plate that are washed into that diameter is 1.3cm.Take metal lithium sheet as negative pole, with Celgard2325 microporous polypropylene membrane for barrier film, with LB315 lithium battery electrolytes for electrolyte, in LB315 lithium battery electrolytes, the mass ratio of DMC, EMC and EC is 1:1:1, then in the glove box being full of argon gas, is assembled into button cell.
In 2.5V ~ 4.5V voltage range, charge and discharge cycles test is carried out to described button cell.As shown in Figure 4 and Figure 5, Fig. 4 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4 to test result
4the charging and discharging curve of/C positive electrode material, Fig. 5 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4
4the cycle performance curve of/C positive electrode material.From Fig. 4 and Fig. 5, the LiMnPO that the embodiment of the present invention 1 is obtained
4the discharge voltage of/C positive electrode material is 3.99V ~ 4.10V, has obvious discharge platform at about 4V, and when charging with 0.05C multiplying power, reversible specific capacity is 159mAh/g, and through 50 circulations, battery capacity conservation rate is more than 95%.Show that anode material for lithium-ion batteries prepared by the present invention has higher specific capacity and capability retention, chemical property is better, thus can improve the performance of lithium ion battery.
Embodiment 2
Be 2.5molL by concentration
-1liOHH
2o solution adds in stirring reaction device, is stirred to pH stablizes with the rotating speed of 600rpm, is then 1.1molL by peristaltic pump by concentration
-1liH
2pO
4solution adds in described stirring reaction device with the charging rate of 0.8mL/min and reacts, wherein, and LiOHH
2o and LiH
2pO
4mol ratio be 2:1, work as LiH
2pO
4after solution adds, then stir 30min with the speed of 300rpm, reaction generates sediment, is carried out by described sediment washing, suction filtration and drying, obtains the Li of white
3pO
4powder.
Be 1:1 according to mol ratio, by described Li
3pO
4powder and MnCl
2be transferred to polyurethane ball-milling pot, add 0.45g ascorbic acid, add 60mL water and 1 again, the mixed solvent of 4-butanediol composition, wherein, described water and 1, the mol ratio of 4-butanediol is 200, carry out liquid phase ball milling 0.5h, obtain mixed solution, then described mixed solution is transferred to rapidly in the hydrothermal reaction kettle of 100mL, logical 5min argon gas (Ar), described hydrothermal reaction kettle is sealed, be be incubated under the condition of 150 DEG C in temperature, room temperature is cooled to after 10h, finally the precipitation in still is washed, suction filtration, and at 80 DEG C vacuum drying, obtain linen product LiMnPO
4.
Take LiMnPO described in 15g
4be placed in ball grinder with 4.5g sucrose, ball milling 5h, then in 600 DEG C, calcine under argon gas atmosphere, obtain LiMnPO after 10h
4/ C positive electrode material.
By the LiMnPO obtained
4/ C positive electrode material carries out X-ray diffraction test, and as shown in Figure 6, Fig. 6 is LiMnPO prepared by the embodiment of the present invention 1 ~ 4 to test result
4the X ray diffracting spectrum of/C positive electrode material.As can be seen from Figure 6, gained LiMnPO
4/ C positive electrode material is lithium manganese phosphate, and purity is high, thing is mutually single, crystal formation integrality is better.
According to the method for embodiment 1, by described LiMnPO
4/ C positive electrode material is assembled into button cell.
According to the method for embodiment 1, charge and discharge cycles test is carried out to described button cell.Test result as shown in Figure 4 and Figure 5.From Fig. 4 and Fig. 5, the LiMnPO that the embodiment of the present invention 2 is obtained
4the reversible specific capacity first of/C positive electrode material is up to 162mAh/g, and through 50 circulations, battery capacity conservation rate is more than 95%.Show that anode material for lithium-ion batteries prepared by the present invention has higher specific capacity and capability retention, chemical property is better, thus can improve the performance of lithium ion battery.
Embodiment 3
Be 1.2molL by concentration
-1li
2sO
4solution adds in stirring reaction device, is stirred to pH stablizes with the rotating speed of 600rpm, is then 1.1molL by peristaltic pump by concentration
-1liH
2pO
4solution adds in described stirring reaction device with the charging rate of 0.8mL/min and reacts, wherein, and Li
2sO
4with LiH
2pO
4mol ratio be 1:1, work as LiH
2pO
4after solution adds, then stir 30min with the speed of 300rpm, reaction generates sediment, is carried out by described sediment washing, suction filtration and drying, obtains the Li of white
3pO
4powder.
Be 1:1 according to mol ratio, by described Li
3pO
4powder and Mn(NO
3)
2be transferred to polyurethane ball-milling pot, add 0.45g ascorbic acid, add the mixed solvent that 60mL water and glycerol form again, wherein, the mol ratio of described water and glycerol is 200, carry out liquid phase ball milling 1.5h, obtain mixed solution, then described mixed solution is transferred to rapidly in the hydrothermal reaction kettle of 100mL, logical 5min argon gas (Ar), described hydrothermal reaction kettle is sealed, be be incubated under the condition of 170 DEG C in temperature, room temperature is cooled to after 10h, finally the precipitation in still is washed, suction filtration, and at 80 DEG C vacuum drying, obtain linen product LiMnPO
4.
Take LiMnPO described in 15g
4be placed in ball grinder with 3.5g ascorbic acid, ball milling 5h, then in 600 DEG C, calcine under argon gas atmosphere, obtain LiMnPO after 10h
4/ C positive electrode material.
By the LiMnPO obtained
4/ C positive electrode material carries out X-ray diffraction test, and test result as shown in Figure 6.As can be seen from Figure 6, gained LiMnPO
4/ C positive electrode material is lithium manganese phosphate, and purity is high, thing is mutually single, crystal formation integrality is better.
According to the method for embodiment 1, by described LiMnPO
4/ C positive electrode material is assembled into button cell.
According to the method for embodiment 1, charge and discharge cycles test is carried out to described button cell.Test result as shown in Figure 4 and Figure 5.From Fig. 4 and Fig. 5, the LiMnPO that the embodiment of the present invention 3 is obtained
4the reversible specific capacity of electric discharge first of/C positive electrode material is up to 159mAh/g, and through 50 circulations, battery capacity conservation rate is more than 95%.Show that anode material for lithium-ion batteries prepared by the present invention has higher specific capacity and capability retention, chemical property is better, thus can improve the performance of lithium ion battery.
Embodiment 4
Be 2.5molL by concentration
-1liNO
3solution adds in stirring reaction device, is stirred to pH stablizes with the rotating speed of 600rpm, is then 1.1molL by peristaltic pump by concentration
-1h
3pO
4solution adds in described stirring reaction device with the charging rate of 0.8mL/min and reacts, wherein, and LiNO
3with H
3pO
4mol ratio be 3:1, work as H
3pO
4after solution adds, then stir 30min with the speed of 300rpm, reaction generates sediment, is carried out by described sediment washing, suction filtration and drying, obtains the Li of white
3pO
4powder.
Be 1:1 according to mol ratio, by described Li
3pO
4powder and MnC
2o
4be transferred to polyurethane ball-milling pot, add 0.45g ascorbic acid, add the mixed solvent that 60mL water and pentaerythrite form again, wherein, the mol ratio of described water and pentaerythrite is 200, carry out liquid phase ball milling 0.5h, obtain mixed solution, then described mixed solution is transferred to rapidly in the hydrothermal reaction kettle of 100mL, logical 5min argon gas (Ar), described hydrothermal reaction kettle is sealed, be be incubated under the condition of 230 DEG C in temperature, room temperature is cooled to after 5h, finally the precipitation in still is washed, suction filtration, and at 80 DEG C vacuum drying, obtain linen product LiMnPO
4.
Take LiMnPO described in 15g
4be placed in ball grinder with 2.5g citric acid, ball milling 5h, then in 600 DEG C, calcine under argon gas atmosphere, obtain LiMnPO after 10h
4/ C positive electrode material.
By the LiMnPO obtained
4/ C positive electrode material carries out X-ray diffraction test, and test result as shown in Figure 6.As can be seen from Figure 6, gained LiMnPO
4/ C positive electrode material is lithium manganese phosphate, and purity is high, thing is mutually single, crystal formation integrality is better.
According to the method for embodiment 1, by described LiMnPO
4/ C positive electrode material is assembled into button cell.
According to the method for embodiment 1, charge and discharge cycles test is carried out to described button cell.Test result as shown in Figure 4 and Figure 5.From Fig. 4 and Fig. 5, the LiMnPO that the embodiment of the present invention 4 is obtained
4the reversible specific capacity first of/C positive electrode material is up to 151mAh/g, and through 50 circulations, battery capacity conservation rate is more than 95%.Show that anode material for lithium-ion batteries prepared by the present invention has higher specific capacity and capability retention, chemical property is better, thus can improve the performance of lithium ion battery.
As seen from the above embodiment, preparation method's technique of anode material for lithium-ion batteries provided by the invention is simple, controlled, with low cost.The present invention can control pattern and the granular size of material by Controlling Technology condition, making the manganese-lithium phosphate anode material synthesized have crystal formation generates complete, and particle is tiny, is uniformly dispersed, high and the capability retention advantages of higher of specific capacity, thus the performance of lithium ion battery can be improved.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (7)
1. a preparation method for anode material for lithium-ion batteries, comprises the following steps:
A) provide nanometer lithium phosphate, described nanometer lithium phosphate has hollow-core construction;
B) ball milling is carried out after the mixed solvent that the nanometer lithium phosphate described step a) provided, soluble manganese source compound, additive and water and polyalcohol form mixes, obtain mixed solution, then by described mixed solution logical inert gas close reactor in, be be incubated under the condition of 150 DEG C ~ 230 DEG C in temperature, obtain lithium manganese phosphate;
C) by described step b) lithium manganese phosphate that obtains carries out ball milling after mixing with carbon-source cpd, through calcining, obtains the anode material for lithium-ion batteries of the coated lithium manganese phosphate of carbon;
Described step b) in, described additive is selected from one or more in citric acid, ascorbic acid, malic acid, lactic acid, oxalic acid and tartaric acid.
2. preparation method according to claim 1, is characterized in that, described step a) in, described nanometer lithium phosphate is prepared in accordance with the following methods:
Li source compound solution is provided, then under agitation adds P source compound solution wherein and react, continue after reaction to stir, after filtration, obtain the nanometer lithium phosphate with hollow-core construction.
3. preparation method according to claim 2, is characterized in that, described step a) in, reaction after continue stir time, the speed of described stirring is 300rpm ~ 800rpm, and the time is 0.5h ~ 3h.
4. preparation method according to claim 1 and 2, is characterized in that, described step b) in, in the mixed solvent that water and polyalcohol form, the mol ratio of described water and polyalcohol is greater than 0 and is less than or equal to 400.
5. preparation method according to claim 1 and 2, it is characterized in that, described step b) in, described polyalcohol is selected from diethylene glycol, 1, one or more in 4-butanediol, ethylene glycol, 1,2-PD, neopentyl glycol, dipropylene glycol, glycerine, pentaerythrite and trimethylolethane.
6. preparation method according to claim 1 and 2, is characterized in that, described step b) in, the time of described ball milling is 0.5h ~ 15h.
7. preparation method according to claim 1 and 2, is characterized in that, described step b) in, the time of described insulation is 7h ~ 36h.
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| CN104638262B (en) * | 2013-11-11 | 2018-07-13 | 新乡学院 | A kind of preparation method of lithium ion battery anode material manganese lithium phosphate |
| CN104577123A (en) * | 2015-02-02 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of cathode material for lithium ion cell |
| CN104779374A (en) * | 2015-04-23 | 2015-07-15 | 天津巴莫科技股份有限公司 | Preparation method of high-performance hollow manganese lithium phosphate for lithium ion powder battery |
| CN105006569B (en) * | 2015-06-03 | 2018-12-25 | 浙江大学 | Nanoscale lithium manganese phosphate material and its preparation method and application |
| CN105070912A (en) * | 2015-07-23 | 2015-11-18 | 东北大学 | Preparation method of spherical lithium ion battery cathode material lithium manganese phosphate |
| CN105513820B (en) * | 2016-01-12 | 2018-03-16 | 浙江大学 | A kind of preparation method of lithium manganese phosphate material of carbon coating and products thereof and application |
| CN106935832A (en) * | 2017-03-31 | 2017-07-07 | 四川浩普瑞新能源材料股份有限公司 | Lithium manganese phosphate composite, its preparation method and lithium ion battery |
| CN107611367B (en) * | 2017-08-04 | 2020-08-18 | 中南大学 | Porous spherical carbon-coated vanadium sodium phosphate composite positive electrode material and preparation method thereof |
| CN110518240A (en) * | 2019-09-04 | 2019-11-29 | 井冈山大学 | A kind of LiMnPO of structure-controllable4Tiny balloon and its preparation method and application |
| CN112018364B (en) * | 2020-09-05 | 2022-10-04 | 河南科技学院 | Equimolar hydrothermal method for preparing LiMnPO 4 Method for preparing composite material and application of composite material in lithium battery |
| CN112652768B (en) * | 2020-10-23 | 2022-05-20 | 有研工程技术研究院有限公司 | Preparation method of lithium manganese phosphate-graphene composite material, lithium manganese phosphate-graphene composite material and application |
| CN113540455B (en) * | 2021-05-31 | 2022-08-19 | 佛山市德方纳米科技有限公司 | Hollow carbon-coated lithium iron phosphate particles and preparation method and application thereof |
| CN115652108B (en) * | 2022-10-31 | 2024-04-12 | 安徽工业大学 | Method for dissolving and recycling lithium cobaltate by eutectic solvent |
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