CN102983334B - Anode material for lithium-ion batteries and preparation method thereof - Google Patents
Anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN102983334B CN102983334B CN201210551815.XA CN201210551815A CN102983334B CN 102983334 B CN102983334 B CN 102983334B CN 201210551815 A CN201210551815 A CN 201210551815A CN 102983334 B CN102983334 B CN 102983334B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula: LiMn shown in formula (I)
1-xm
xpO
4(I); Wherein, 0 < x < 0.2; M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.Anode material for lithium-ion batteries provided by the invention comprises sheet carbon compound phosphoric acid manganese lithium, and all sheet carbon compound phosphoric acid manganese lithiums are radially arranged in many wheels, and the positive electrode of this shape shortens the evolving path of lithium ion in lithium manganese phosphate particle; The positive electrode of this shape has the specific area sent to simultaneously, make lithium ion deintercalation and transmit rapider, and it is more abundant and even that positive electrode mixes with battery conductive additive, thus make anode material for lithium-ion batteries provided by the invention have higher discharge capacity and cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, particularly relate to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
The main composition material of lithium ion battery comprises electrolyte, isolated material, positive and negative pole material etc.Positive electrode occupies larger proportion, because the performance of positive electrode directly affects the performance of lithium ion battery, its cost also directly determines battery cost height.Prior art research shows, the phosphate system material of olivine-type structure is as the positive electrode of lithium ion battery, security performance and cycle life these two aspects are obviously better than traditional layer structure material, as cobalt acid lithium, lithium nickelate and ternary material etc., its representative materials LiFePO4 (LiFePO
4) extensively studied confirmation by academia and industrial circle, and be widely used in the field such as electrokinetic cell and energy-storage battery.But the voltage platform of opposing metallic lithium 3.4V defines the lifting of LiFePO4 energy density, thus affects the market competitiveness of this material.
In order to improve the energy density of phosphate system material, prior art has developed lithium manganese phosphate (LiMnPO
4) material, with LiFePO4 (LiFePO
4) compare, current potential can be improved 0.7V by lithium manganese phosphate, and it also has the theoretical specific capacity of 171mAh/g, makes it be expected to the positive electrode of the lithium ion battery with high energy density becoming a new generation.But electronic conductivity and the lithium ion diffusion rate of lithium manganese phosphate material are lower than LiFePO4, therefore the lithium manganese phosphate material of non-modified cannot meet practical application needs at all.
In order to improve electronic conductivity and the lithium ion diffusion rate of manganese-lithium phosphate anode material, prior art is coated mainly through carbon, doped with metal elements and material granule nanometer carry out modification to manganese-lithium phosphate anode material, thus improves the chemical property of lithium manganese phosphate material.HuihuaYi(ElectrochimicaActa, 2011,56 (11): 40520 ~ 4057.) etc. people adopts Solid phase synthesis manganese-lithium phosphate anode material, by the LiH of stoichiometric proportion
2pO
4, MnC
4h
6o
44H
2o, FeC
2o
42H
2o, MgC
4h
6o
44H
2o, H
2c
2o
42H
2o and mass fraction are abundant ball milling 6h after the sucrose mixing of 14wt.%, then under argon gas atmosphere protection, 800 DEG C of high-temperature calcination 10h, obtaining chemical composition is LiMn
0.9fe
0.05mg
0.05pO
4the material of/C, the discharge capacity first obtaining 0.1C through electrochemical property test is 140mAh/g.This solid phase method technique is simple, and suitability for industrialized production is convenient, but still to there is particle large for the material prepared by the method, and particle diameter heterogeneity and the coated problem such as imperfect of carbon, this will have a strong impact on the cycle performance of material, the performance such as high rate performance and high/low temperature.In order to control the granular size of positive electrode, ThierryDrezen(JournalofPowerSources, 2007,174 (2): 949 ~ 953.) etc. people controls material granule particle diameter by adopting sol-gal process and regulation and control sintering temperature, first lithium acetate, manganese acetate and ammonium dihydrogen phosphate are dissolved in deionized water, then add chelating agent glycolic wherein, between 60 DEG C ~ 75 DEG C, obtain gel, then at different temperature (400 DEG C ~ 800 DEG C), calcine 3h and obtain LiMnPO
4material.Characterize through ESEM, minimum at the material particle size of 520 DEG C of calcining preparations is 140nm, and its 0.1C first discharge capacity is 116mAh/g.Although collosol and gel can make reactant that intermolecular mixing and reaction occur, can control the particle diameter of material, this low-temperature bake process can reduce the crystallinity of material, thus causes material structure bad stability and chemical property sharply to worsen.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium-ion batteries and preparation method thereof, anode material for lithium-ion batteries provided by the invention has higher structural stability and chemical property.
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula shown in formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0 < x < 0.2;
M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.
Preferably, 0.01≤x≤0.19.
Preferably, described M is a kind of in Ti, Fe, Mg, Al and Cr.
Preferably, the thickness of described sheet carbon compound phosphoric acid manganese lithium is less than or equal to 300nm.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
By P source compound, manganese source compound, mix in water containing M compound, Li source compound, carbon-source cpd and surfactant, obtain suspension, described M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb;
In confined conditions, described suspension is heated, obtains positive electrode material precursor;
In an inert atmosphere, described positive electrode material precursor is carried out roasting, obtains anode material for lithium-ion batteries.
Preferably, described P source compound is one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium;
Described manganese source compound is one or more in manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide;
Described is one or more in the oxide of M, hydroxide, nitrate, acylate containing M compound;
Described Li source compound is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium;
Described carbon-source cpd is one or more in conductive black, carbon nano-tube, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide;
Preferably, described surfactant is one or more in citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, lauryl sodium sulfate, neopelex, amino acid, Qu Latong and sulfonic acid.
Preferably, described P source compound, manganese source compound, be (1 ~ 1.1) containing the mol ratio of phosphorus, manganese, M and Li in M compound, Li source compound: (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1);
The quality of described carbon-source cpd is P source compound, manganese source compound, 5wt% ~ 15wt% containing M compound and Li source compound gross mass;
The quality of described surfactant is P source compound, manganese source compound, 1wt% ~ 10wt% containing M compound and Li source compound gross mass.
Preferably in, the solid content of described suspension is 20wt% ~ 40wt%.
Preferably, the temperature of described heating is 150 DEG C ~ 250 DEG C;
The time of described heating is 5h ~ 15h.
Preferably, the temperature of described roasting is 500 DEG C ~ 700 DEG C;
The time of described roasting is 2h ~ 8h.
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula: LiMn shown in formula (I)
1-xm
xpO
4(I); Wherein, 0 < x < 0.2; M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.Anode material for lithium-ion batteries provided by the invention is made up of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium radially arranges, such oriented growth shortens the evolving path of lithium ion in lithium manganese phosphate particle, improves the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition increases the specific area of material simultaneously, thus expand contact and the wetted area of positive electrode and electrolyte, make lithium ion deintercalation and transmit rapider, and make positive electrode more abundant and even with mixing of battery conductive additive, further increasing the conductance of positive electrode, thus make anode material for lithium-ion batteries provided by the invention have higher discharge capacity and cycle performance, make it have higher stability.Experimental result shows, the discharge capacity first of anode material for lithium-ion batteries provided by the invention can reach 160mAh/g.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the positive electrode that the embodiment of the present invention 1 obtains;
Fig. 2 is that the positive electrode that the embodiment of the present invention 1 obtains amplifies 10.0k stereoscan photograph doubly;
Fig. 3 is that the positive electrode that the embodiment of the present invention 1 obtains amplifies 50.0k stereoscan photograph doubly;
Fig. 4 is the positive electrode that the embodiment of the present invention 1 obtains is the transmission electron microscope photo of 5.6mm at WD;
The projection electromicroscopic photograph of Fig. 5 to be positive electrode that the embodiment of the present invention 1 obtains at WD be 4.6mm;
Fig. 6 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 1 and comparative example 1 obtain;
Fig. 7 is the first discharge specific capacity curve of the positive electrode that the embodiment of the present invention 2 obtains;
Fig. 8 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 3 obtains.
Embodiment
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material composition, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula shown in formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0 < x < 0.2;
M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium, these sheet carbon compound phosphoric acid manganese lithiums radially oriented growth, obtains the anode material for lithium-ion batteries of the 3-D solid structure with globoid or spheroid form.In the present invention, described each radially arranges, it can be irregular radial arrangement, preferably each sheet carbon compound phosphoric acid manganese lithium material interlocks but nonoverlapping arrangement, the present invention do not get rid of yet have sheet carbon compound phosphoric acid manganese lithium material stretcher radially to arrange in multi-disc carbon compound phosphoric acid manganese lithium material on, participate in the stereoscan photograph of the positive electrode shown in Fig. 2, anode material for lithium-ion batteries provided by the invention is as corolla shape, and sheet carbon compound phosphoric acid manganese lithium material is as petal.In the present invention, the oriented growth of sheet carbon compound phosphoric acid manganese lithium shortens the evolving path of lithium ion in lithium manganese phosphate particle, improves the conductivity of positive electrode; And radially staggered but the structure of overlapping arrangement do not increase the specific area of positive electrode, thus expand contact and the infiltration of positive electrode and electrolyte, make lithium ion deintercalation and transmit rapider, make positive electrode more all fully even with mixing of battery conductive agent, improve the conductivity of positive electrode, thus make anode material for lithium-ion batteries provided by the invention have higher discharge capacity and cycle performance.
In the present invention, described sheet carbon compound phosphoric acid manganese lithium material preferred arrangement obtains the positive electrode of sphere-like or globoid shape, the thickness of described sheet carbon compound phosphoric acid manganese lithium material is preferably less than or equal to 300nm, is more preferably 20nm ~ 250nm, most preferably is 30nm ~ 200nm;
In the present invention, described lithium manganese phosphate has chemical formula shown in formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0 < x < 0.2, preferred 0.01≤x≤0.19;
M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb, is preferably in Ti, Fe, Mg, Al and Cr a kind of, is more preferably a kind of in Ti, Fe and Mg.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
By P source compound, manganese source compound, mix in water containing M compound, Li source compound, carbon-source cpd and surfactant, obtain suspension, described M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb;
In confined conditions, described suspension is heated, obtains positive electrode material precursor;
In an inert atmosphere, described positive electrode material precursor is carried out roasting, obtains anode material for lithium-ion batteries.
The present invention with P source compound, manganese source compound, containing M compound, Li source compound, carbon-source cpd and surfactant for raw material, first carry out after being mixed heating reaction, obtain positive electrode material precursor; Again the positive electrode material precursor obtained is carried out roasting, obtain anode material for lithium-ion batteries.The present invention is using surfactant as the raw material preparing positive electrode, surfactant can regulate the direction of growth and the structure thereof of positive electrode, the lithium manganese phosphate of carbon compound is radially grown, the one end of the sheet carbon compound phosphoric acid manganese lithium obtained links together, carbon compound phosphoric acid manganese lithium radially oriented growth centered by one end that it links together, shorten the evolving path of lithium ion in lithium manganese phosphate particle, and the positive electrode obtained has larger specific area, improve the conductivity of material, thus make the positive electrode obtained have higher discharge capacity and cycle performance.
The present invention, first by P source compound, manganese source compound, mix in water containing M compound, Li source compound, carbon-source cpd and surfactant, obtains suspension, and described M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.The present invention to P source compound, manganese source compound, do not have special restriction containing the order by merging of M compound, Li source compound, carbon-source cpd and surfactant, adopts the order by merging of supending well known to those skilled in the art;
In the present invention, described P source compound be preferably in phosphoric acid or phosphate one or more, be more preferably one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium, most preferably be one or more in phosphoric acid, diammonium hydrogen phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium, be the most preferably one or both in phosphoric acid and diammonium hydrogen phosphate;
Described manganese source compound be preferably in manganese salt, the oxide of manganese and the hydroxide of manganese one or more, be more preferably one or more in manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide, most preferably be in manganese carbonate, manganese acetate, manganese dioxide, manganous hydroxide one or more, be the most preferably in manganese carbonate, manganese acetate and manganese dioxide one or more;
Described M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb, is preferably in Ti, Fe, Mg, Al and Cr a kind of, is more preferably a kind of in Ti, Fe and Mg; Described containing M compound be preferably in the oxide of M, hydroxide, nitrate, acylate one or more, be more preferably the oxide of M;
Described Li source compound be preferably in the hydroxide of lithium salts and lithium one or more, be more preferably one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium, most preferably be in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium phosphate one or more, be the most preferably in lithium hydroxide, lithium carbonate and lithium acetate one or more;
Described carbon-source cpd can be DIC, also can be organic carbon, be preferably one or more in conductive black, carbon nano-tube, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide, be more preferably in carbon nano-tube, acetylene black, sucrose, polyvinyl alcohol, polysaccharide and phenolic resins one or more, most preferably be in carbon nano-tube, sucrose and polyvinyl alcohol one or more;
Described surfactant can be anion surfactant, also can be cationic surfactant, it can also be zwitterionic surfactant, it can also be non-ionic surface active agent, be preferably citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, lauryl sodium sulfate, neopelex, amino acid, one or more in Qu Latong and sulfonic acid, be more preferably stearic acid, hexadecane and trimethylammonium bromide, neopelex, one or more in amino acid and Qu Latong, most preferably be Qu Latong, one or more in hexadecane and trimethylammonium bromide and neopelex,
In the present invention, described P source compound, manganese source compound, containing phosphorus, manganese, M and lithium in M compound, Li source compound mol ratio be preferably (0.8 ~ 1.5): (0.5 ~ 1.5): (0.5 ~ 0): (0.5 ~ 1.5), described is not 0 containing M compound, is more preferably (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0.01): (1 ~ 1.1); The Functionality, quality and appealing design of described carbon-source cpd elects P source compound, manganese source compound, 5wt%15wt% containing M compound and Li source compound gross mass as, is more preferably 8wt% ~ 12wt%; The Functionality, quality and appealing design of described surfactant elects P source compound, manganese source compound, 1wt% ~ 10wt% containing M compound and Li source compound gross mass as, is more preferably 3wt% ~ 8wt%;
In the present invention, the solid content of described suspension is preferably 10wt% ~ 50wt%, is more preferably 15wt% ~ 45wt%, most preferably is 20wt% ~ 40wt%.
After obtaining suspension, described suspension in confined conditions, heats, obtains positive electrode material precursor by the present invention.The present invention does not have special restriction to providing of described airtight condition, adopts airtight condition well known to those skilled in the art, reacts as the suspension that technique scheme obtains being placed in airtight reactor; In the present invention, the temperature of described heating is preferably 120 DEG C ~ 280 DEG C, is more preferably 130 DEG C ~ 260 DEG C, most preferably is 150 DEG C ~ 150 DEG C; The time of described heating is preferably 3h ~ 20h, is more preferably 4h ~ 18h, most preferably is 5h ~ 15h.
After completing the heating to suspension, reaction system is preferably cooled to room temperature by the present invention, is then carried out by the solid obtained washing, filtering and drying, obtains positive electrode material precursor.The method of the present invention to described washing, filtration and drying does not have special restriction, adopts the technical scheme of washing well known to those skilled in the art, filtration and drying.
After obtaining positive electrode material precursor, described positive electrode material precursor, in inert gas atmosphere, is carried out roasting, is obtained anode material for lithium-ion batteries by the present invention.The present invention does not have special restriction to described inert gas, adopts inert gas well known to those skilled in the art, as described in inert gas can be nitrogen, also can be helium; The present invention preferably carries out roasting in a nitrogen atmosphere; The temperature of described roasting is preferably 450 DEG C ~ 750 DEG C, is more preferably 480 DEG C ~ 720 DEG C, is more preferably 500 DEG C ~ 700 DEG C; The time of described roasting is preferably 2h ~ 10h, is more preferably 2h ~ 8h.
Reaction system is preferably cooled to room temperature after completing the roasting to positive electrode material precursor by the present invention, obtains anode material for lithium-ion batteries.
The present invention forms the positive electrode obtained and the sign of pattern, and detailed process is as follows:
The model adopting Japanese Shimadzu to produce is that the x-ray powder diffraction instrument (XRD) of XRD-6000 characterizes anode material for lithium-ion batteries provided by the invention, result shows, impurity peaks is not had in the XRD spectra obtained, only have the characteristic peak of lithium manganese phosphate, this illustrates that the positive electrode that method provided by the invention obtains is lithium manganese phosphate;
The model that the present invention adopts HIT to produce is the field emission scanning electron microscope (SEM) of S-4800 carries out pattern sign to anode material for lithium-ion batteries provided by the invention, result shows, positive electrode provided by the invention is the spheroid be radially made up of multi-disc laminated structure, and one end of described laminated structure links together as the center of spheroid;
The model that the present invention adopts Merck & Co., Inc of the U.S. to produce is that the specific surface measuring and analysing meter of ASAP-2020M characterizes anode material for lithium-ion batteries provided by the invention, and result shows that the specific area of positive electrode provided by the invention can reach 45.6m
2/ g.
The positive electrode obtained combination is obtained lithium ion battery by the present invention, and investigated the electric property of the positive electrode obtained, detailed process is as follows:
Anode material for lithium-ion batteries provided by the invention is mixed by the mass ratio of 90:5:5 with acetylene black conductor and Kynoar binding agent respectively, the mixture obtained is applied in aluminum foil current collector, after 80 DEG C of oven dry, obtains with sheet-punching machine the electrode slice that diameter is 1cm; Using the electrode slice that obtains as positive pole, negative pole is metal lithium sheet, and barrier film is Celgard2400, and electrolyte solution is EC, DMC, EMC and molar concentration is 1mol/LLiPF
6mixed solution, the model of producing in German Braun company is the inert atmosphere glove box (O of UNlab
2and H
2the content of O is all less than 1ppm) in assembling obtain CR2032 button half-cell;
The model that the present invention adopts Wuhan Lan electricity company to produce is that the battery test system of CT2001A carries out electrochemical property test to the CR2032 button half-cell that the present invention obtains, the voltage range of test condition is 2.0 ~ 4.5V, current density converts by 0.1C=17mA/g, result shows, positive electrode provided by the invention is under room temperature 0.1C electric current, and first discharge specific capacity reaches 160mAh/g.
The invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula: LiMn shown in formula (I)
1-xm
xpO
4(I); Wherein, 0 < x < 0.2; M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.Anode material for lithium-ion batteries provided by the invention is made up of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium radially arranges, such oriented growth shortens the evolving path of lithium ion in lithium manganese phosphate particle, improves the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition increases the specific area of material simultaneously, thus expand contact and the wetted area of positive electrode and electrolyte, make lithium ion deintercalation and transmit rapider, and make positive electrode more abundant and even with mixing of battery conductive additive, further increasing the conductance of positive electrode, thus make anode material for lithium-ion batteries provided by the invention have higher discharge capacity and cycle performance, make it have higher stability.
In order to further illustrate the present invention, below in conjunction with embodiment, anode material for lithium-ion batteries provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as limiting the scope of the present invention.
In the following example, the model adopting Japanese Shimadzu to produce is that x-ray powder diffraction instrument (XRD) composition to anode material for lithium-ion batteries provided by the invention of XRD-6000 characterizes; The model adopting HIT to produce is the field emission scanning electron microscope (SEM) of S-4800 carries out pattern sign to anode material for lithium-ion batteries provided by the invention; The model adopting Merck & Co., Inc of the U.S. to produce is that the specific area of specific surface measuring and analysing meter to anode material for lithium-ion batteries provided by the invention of ASAP-2020M characterizes; The model adopting Wuhan Lan electricity company to produce is that the battery test system of CT2001A carries out electrochemical property test to the CR2032 button half-cell that the present invention obtains.
Embodiment 1
Be the phosphoric acid of 85% by the mass concentration of 115.3g, the iron oxide of the manganese carbonate of 93.1g, 15.17g, the lithium hydroxide of 46.16g, the sucrose of 40.46g and 2.7g neopelex be scattered in the deionized water of 730g, be made into the suspension that solid content is 30%; Then above-mentioned suspension is added in reactor, be heated to 200 DEG C of reaction 15h in confined conditions, after question response completes and is cooled to room temperature, the solid obtained carried out wash, filter and after drying, obtain manganese phosphate lithium front body powder; The manganese phosphate lithium front body powder high-temperature roasting 8h under nitrogen atmosphere protection will obtained again, sintering temperature is 500 DEG C, is then cooled to room temperature and obtains anode material for lithium-ion batteries.
The anode material for lithium-ion batteries obtained is carried out X-ray diffraction analysis by the present invention, as shown in Figure 1, Fig. 1 is the XRD spectra of the positive electrode that the embodiment of the present invention 1 obtains to result, as seen from Figure 1, the positive electrode that the present embodiment obtains is lithium manganese phosphate, does not have other impurity peaks; It is LiMn that the present invention detects the molecular formula that its composition obtains positive electrode
0.81fe
0.19pO
4-C;
The anode material for lithium-ion batteries obtained is carried out ESEM scanning analysis by the present invention, result as shown in Figures 2 and 3, Fig. 2 is that the positive electrode that the embodiment of the present invention 1 obtains amplifies 10.0k stereoscan photograph doubly, Fig. 3 is that the positive electrode that the embodiment of the present invention 1 obtains amplifies 50.0k stereoscan photograph doubly, as can be seen from Fig. 2 and Fig. 3, the anode material for lithium-ion batteries that the present invention prepares comprises multi-disc laminated structure, all laminated structures surround spheroid, the radially cross laminates arrangement of these lamellar structures, obtain the anode material for lithium-ion batteries of the 3-D solid structure had as corolla shape globoid,
The anode material for lithium-ion batteries obtained is carried out transmission electron microscopy analysis by the present invention, result as shown in Figure 4 and Figure 5, Fig. 4 is the positive electrode that the embodiment of the present invention 1 obtains is the transmission electron microscope photo of 5.6mm at WD, the projection electromicroscopic photograph of Fig. 5 to be positive electrode that the embodiment of the present invention 1 obtains at WD be 4.6mm, as can be seen from Fig. 4 and Fig. 5, the positive electrode that the present invention obtains by multi-disc flaky material radially cross arrangement obtain, and the thickness obtaining flaky material is 58.05nm;
It is 45.6m that the present invention detects the specific area obtaining anode material for lithium-ion batteries prepared by the present embodiment
2/ g.
The present invention detects the chemical property of anode material for lithium-ion batteries, and detailed process is as follows:
The positive electrode obtained by the present embodiment mixes by 90:5:5 mass ratio with acetylene black conductor and Kynoar binding agent respectively, is applied in aluminum foil current collector, obtains the electrode slice that diameter is 1cm after 80 DEG C of oven dry with sheet-punching machine; Using this electrode slice as positive pole, negative pole is metal lithium sheet, and barrier film is Celgard2400, and electrolyte solution is EC, DMC, EMC and molar concentration is the LiPF of 1mol/L
6mixed solution, at German Braun company UNlab type inert atmosphere glove box (O
2and H
2the content of O is all less than 1ppm) in be assembled into and obtain CR2032 button half-cell;
The present invention adopts the blue electric CT2001A type battery test system in Wuhan to carry out electrochemical property test to CR2032 button half-cell, voltage range is 2.0 ~ 4.5V, current density converts by 0.1C=17mA/g, test result as shown in Figure 6, Fig. 6 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 1 and comparative example 1 obtain, wherein, curve a is the first discharge specific capacity curve of the positive electrode that the embodiment of the present invention 1 obtains, as can be seen from curve a, anode material for lithium-ion batteries provided by the invention is under room temperature 0.1C electric current, first discharge specific capacity reaches 160mAh/g, there is higher discharge capacity, obviously be better than the positive electrode prepared by comparative example 1.
Comparative example 1
Be the phosphoric acid of 85% by 115.3g mass concentration, the sucrose of the manganese carbonate of 93.1g, the iron oxide of 15.17g, the lithium hydroxide of 46.16g and 40.46g is scattered in the deionized water of 728g, be made into the suspension that solid content is 30%; Then above-mentioned suspension is added in reactor, be heated to 200 DEG C of reaction 15h in confined conditions, after question response completes and is cooled to room temperature, the solid obtained is carried out wash, filter and drying, obtain manganese phosphate lithium front body powder; Then the manganese phosphate lithium front body powder high-temperature roasting 8h under nitrogen atmosphere protection will obtained again, sintering temperature is 500 DEG C, is then cooled to room temperature and obtains anode material for lithium-ion batteries.
The anode material for lithium-ion batteries obtained is carried out XRD analysis by the present invention, and result shows, the positive electrode that this comparative example obtains is carbon compound phosphoric acid manganese lithium, and its molecular formula is LiMn
0.81fe
0.19pO
4-C;
The anode material for lithium-ion batteries obtained is carried out SEM scanning analysis by the present invention, and result shows, the positive electrode that this comparative example obtains is graininess;
The present invention detects the chemical property of anode material for lithium-ion batteries according to the technical scheme described in embodiment 1, and test result as shown in Figure 6.Fig. 6 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 1 and comparative example 1 obtain, wherein, curve b is the first discharge specific capacity curve of the positive electrode that comparative example 1 of the present invention obtains, can find out by curve a and curve b is compared example, anode material for lithium-ion batteries provided by the invention has higher discharge capacity.
Embodiment 2
Being drawn to lead to by the lithium carbonate of the titanium dioxide of the manganese acetate of the diammonium hydrogen phosphate of 138.66g, 220.58g, 7.98g, 38.79g, the sucrose of 20.3g and 20.3g song is scattered in the deionized water of 670g, is made into the suspension that solid content is 40%; Then above-mentioned suspension is added in reactor, be heated to 150 DEG C of reaction 10h in confined conditions, after question response completes and is cooled to room temperature, the solid obtained is carried out wash, filter and drying, obtain manganese phosphate lithium front body powder; Then the manganese phosphate lithium front body powder high-temperature roasting 5h under nitrogen atmosphere protection will obtained again, sintering temperature is 600 DEG C, is then cooled to room temperature and obtains anode material for lithium-ion batteries.
The positive electrode obtained is carried out XRD analysis by the present invention, and result shows, the positive electrode that the embodiment of the present invention 2 obtains is carbon compound phosphoric acid manganese lithium, and its molecular formula is LiMn
0.9ti
0.1pO
4-C;
The positive electrode obtained is carried out SEM scanning analysis by the present invention, result shows, the positive electrode that the present invention obtains comprises multi-disc sheet carbon compound phosphoric acid manganese lithium, all sheet carbon compound phosphoric acid manganese lithium composition sphere structures, the radially cross laminates arrangement of these sheet carbon compound phosphoric acid manganese lithiums, obtains the anode material for lithium-ion batteries with 3-D solid structure as corolla shape globoid;
The positive electrode obtained is carried out TEM scanning analysis by the present invention, and result shows, in the positive electrode that the present embodiment obtains, the thickness of sheet carbon compound phosphoric acid manganese lithium is 100nm;
The present invention detects the chemical property obtaining anode material for lithium-ion batteries according to the technical scheme described in embodiment 1, result as shown in Figure 7, Fig. 7 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 2 obtains, as seen from Figure 7, anode material for lithium-ion batteries provided by the invention has higher discharge capacity.
Embodiment 3
The lithium acetate of the magnesium oxide of the manganese dioxide of the diammonium hydrogen phosphate of 126.53g, 86.07g, 0.4g, 65.99g, the polyvinyl alcohol of 27.9g and 27.8g softex kw are scattered in the deionized water of 1336g, are made into the suspension that solid content is 20%; Then above-mentioned suspension is added in reactor, be heated to 250 DEG C of reaction 5h in confined conditions, after question response completes and is cooled to room temperature, the solid obtained is carried out wash, filter and drying, obtain manganese phosphate lithium front body powder; Then the manganese phosphate lithium front body powder high-temperature roasting 2h under nitrogen atmosphere protection will obtained again, sintering temperature is 700 DEG C, is then cooled to room temperature and obtains anode material for lithium-ion batteries.
The positive electrode obtained is carried out XRD analysis by the present invention, and result shows, the positive electrode that the embodiment of the present invention 2 obtains is carbon compound phosphoric acid manganese lithium, and its molecular formula is LiMn
0.99mg
0.01pO
4-C;
The positive electrode obtained is carried out SEM scanning analysis by the present invention, result shows, the positive electrode that the present invention obtains comprises multi-disc sheet carbon compound phosphoric acid manganese lithium, all sheet lithium manganese phosphate composition sphere structures, the radially cross laminates arrangement of these sheet carbon compound phosphoric acid manganese lithiums, obtains the anode material for lithium-ion batteries with 3-D solid structure as corolla shape globoid;
The positive electrode obtained is carried out TEM scanning analysis by the present invention, and result shows, in the positive electrode that the present embodiment obtains, the thickness of sheet carbon compound phosphoric acid manganese lithium is 150nm;
The present invention detects the chemical property obtaining anode material for lithium-ion batteries according to the technical scheme described in embodiment 1, result as shown in Figure 8, Fig. 8 is the positive electrode first discharge specific capacity curve that the embodiment of the present invention 3 obtains, as seen from Figure 8, anode material for lithium-ion batteries provided by the invention has higher discharge capacity.
As seen from the above embodiment, the invention provides a kind of anode material for lithium-ion batteries, comprise multi-disc sheet carbon compound phosphoric acid manganese lithium material, described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially arranges; Described lithium manganese phosphate has chemical formula: LiMn shown in formula (I)
1-xm
xpO
4(I); Wherein, 0 < x < 0.2; M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.Anode material for lithium-ion batteries provided by the invention is made up of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium radially arranges, such oriented growth shortens the evolving path of lithium ion in lithium manganese phosphate particle, improves the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition increases the specific area of material simultaneously, thus expand contact and the wetted area of positive electrode and electrolyte, make lithium ion deintercalation and transmit rapider, and make positive electrode more abundant and even with mixing of battery conductive additive, further increasing the conductance of positive electrode, thus make anode material for lithium-ion batteries provided by the invention have higher discharge capacity and cycle performance, make it have higher stability.
The above is only the preferred embodiment of the present invention; 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 make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a preparation method for corolla shape anode material for lithium-ion batteries, comprises the following steps:
By P source compound, manganese source compound, mix in water containing M compound, Li source compound, carbon-source cpd and surfactant, obtain suspension, described M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb; The solid content of described suspension is 10wt% ~ 50wt%;
Described P source compound, manganese source compound, be (1 ~ 1.1) containing the mol ratio of phosphorus, manganese, M and lithium in M compound, Li source compound: (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1);
The quality of described carbon-source cpd is P source compound, manganese source compound, 5wt% ~ 15wt% containing M compound and Li source compound gross mass;
The quality of described surfactant is P source compound, manganese source compound, 1wt% ~ 10wt% containing M compound and Li source compound gross mass;
In confined conditions, described suspension is heated, obtains positive electrode material precursor;
In inert gas atmosphere, described positive electrode material precursor is carried out roasting, obtains anode material for lithium-ion batteries;
Described corolla shape anode material for lithium-ion batteries comprises multi-disc sheet carbon compound phosphoric acid manganese lithium material, and described multi-disc sheet carbon compound phosphoric acid manganese lithium material radially, interlock not overlapping arrangement; Described lithium manganese phosphate has chemical formula shown in formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0 < x < 0.2;
M is a kind of in Ti, Co, Fe, Mg, Al, Cr and Nb.
2. preparation method according to claim 1, is characterized in that, 0.01≤x≤0.19.
3. preparation method according to claim 1, is characterized in that, described M is a kind of in Ti, Fe, Mg, Al and Cr.
4. preparation method according to claim 1, is characterized in that, the thickness of described sheet carbon compound phosphoric acid manganese lithium is less than or equal to 300nm.
5. preparation method according to claim 1, is characterized in that, described P source compound is one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium;
Described manganese source compound is one or more in manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide;
Described is one or more in the oxide of M, hydroxide, nitrate, acylate containing M compound;
Described Li source compound is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium;
Described carbon-source cpd is one or more in conductive black, carbon nano-tube, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide.
6. preparation method according to claim 1, it is characterized in that, described surfactant is one or more in citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, lauryl sodium sulfate, neopelex, amino acid, Qu Latong and sulfonic acid.
7. preparation method according to claim 1, is characterized in that, the temperature of described heating is 120 DEG C ~ 280 DEG C;
The time of described heating is 3h ~ 20h.
8. preparation method according to claim 1, is characterized in that, the temperature of described roasting is 450 DEG C ~ 750 DEG C;
The time of described roasting is 2h ~ 10h.
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| CN103337626B (en) * | 2013-04-27 | 2015-12-23 | 上海交通大学 | LiFe xm 1-xpO 4/ mesoporous carbon composite material and preparation method thereof |
| CN103594712B (en) * | 2013-07-18 | 2015-09-16 | 横店集团东磁股份有限公司 | A kind of metal-doped coated lithium manganese phosphate of oxidation conductive carbon black and preparation method thereof |
| CN103474656A (en) * | 2013-07-22 | 2013-12-25 | 浙江瓦力新能源科技有限公司 | Preparation method for metal-doped lithium/carbon manganese phosphate composite from manganese phosphate |
| CN103606678A (en) * | 2013-12-09 | 2014-02-26 | 哈尔滨工业大学 | Preparation method of lithium manganese phosphate-conductive polymer for anode material for lithium ion battery |
| CN104900877A (en) * | 2015-06-09 | 2015-09-09 | 天津巴莫科技股份有限公司 | Preparing method for LiFexMn(1-x)PO4/C for lithium-ion batteries |
| CN105110310B (en) * | 2015-08-13 | 2018-06-19 | 天津巴莫科技股份有限公司 | The preparation method of lithium-ion-power cell lithium manganese phosphate |
| CN108269995B (en) * | 2016-12-30 | 2022-08-26 | 广东天劲新能源科技股份有限公司 | Preparation method of ternary cathode material with adjustable and controllable crystal structure |
| CN108400330B (en) * | 2018-03-08 | 2020-07-14 | 蒋央芳 | Preparation method of carbon-doped manganese (III) phosphate |
| CN109888282A (en) * | 2019-04-02 | 2019-06-14 | 骆驼集团武汉光谷研发中心有限公司 | A kind of lithium iron phosphate positive material and preparation method thereof |
| CN110931773A (en) * | 2019-11-15 | 2020-03-27 | 西安和光明宸科技有限公司 | Preparation method of battery positive electrode material |
| CN111943285B (en) * | 2020-08-19 | 2022-10-14 | 浙江帕瓦新能源股份有限公司 | Nano lithium-rich manganese-based positive electrode material, precursor and base material thereof, and preparation method |
| CN113582220A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | TiO 22Preparation method of/carbon composite interlayer |
| CN114212764B (en) * | 2021-11-30 | 2023-06-30 | 厦门厦钨新能源材料股份有限公司 | Phosphate positive electrode material precursor, preparation method and application thereof |
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