CN102931405B - Lithium manganese phosphate cathode material and preparation method thereof - Google Patents
Lithium manganese phosphate cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lithium manganese phosphate cathode material which comprises carbon and lithium manganese phosphate with a molecular formula (I): LiMn1-xMxPO4 (I), wherein x is greater than or equal to 0 and less than or equal to 0.2, and M is selected from any one of Ti, Co, Fe, Mg, Al, Cr and Nb. The lithium manganese phosphate cathode material disclosed by the invention is of a hollow ball structure, and the hollow ball structure is made of sheet-like primary particles. In the lithium manganese phosphate cathode material, the diffusion path of lithium ions in lithium manganese phosphate particles is shortened by the sheet-like oriented growth of the primary particles, so that the diffusion velocity is increased. The hollow ball structure is more beneficial to immersion and storage of electrolyte and an electrode material, so that deintercalation and transmission processes of the lithium ions are more convenient and faster, and the discharging capacity and the cycling performance of the lithium manganese phosphate material are enhanced.
Description
Technical field
The present invention relates to lithium ion battery material technical field, particularly relate to a kind of manganese-lithium phosphate anode material and preparation method thereof.
Background technology
Lithium ion battery owing to having that operating voltage is high, specific energy is large, self discharge is little and the advantage such as low in the pollution of the environment, and is widely used in civil and military field.Wherein the development of positive electrode technology is the key factor of lithium ion battery technology progress.
In existing positive electrode, Stability Analysis of Structures, security performance are excellent owing to having for polyanion phosphoric acid salt material, the advantage such as to have extended cycle life and receiving much attention, and widely used is at present LiFePO4 (LiFePO
4) material, but the voltage platform of LiFePO4 3.4V seriously limits the raising of battery energy density, thus the application of its market is restricted.By contrast, lithium manganese phosphate (LiMnPO
4) voltage platform of positive electrode opposing metallic lithium is 4.1V, not only exceed 0.7V than the voltage of LiFePO 4 material, and the burning voltage window of the existing commercialization electrolyte system of this voltage conforms, this means under same capacity performance condition, is that the energy density of the lithium ion battery of positive electrode at least will improve 20% than ferric phosphate lithium cell with lithium manganese phosphate.Although lithium manganese phosphate material has the advantage on energy density and cost, its electronic conductivity and lithium ion diffusion rate lower, make the lithium manganese phosphate material of non-modified cannot meet practical application needs.In order to meet its application demand, just modification must be carried out to it, to improve chemical property.
At present, people improve the electronic conductivity of manganese-lithium phosphate anode material mainly through coated with conductive network and material granule nanometer and shorten lithium ion the evolving path, thus improve its chemical property.There is bibliographical information, the coated lithium manganese phosphate material of carbon (Advanced Powder Technology can be prepared by the method for presoma spraying cracking and subsequent high temperature calcining, 2010,21:187 ~ 196), the conductive carbon network layer being coated on lithium manganese phosphate particle top layer improves the chemical property of material to a certain extent, but the lithium manganese phosphate material chemical property prepared by the method is general, the room temperature discharge capacity of 0.05C is only 70mAh/g, and its preparation method is complicated, needs of production can not be met.Prior art also disclosed technology (the Journal of PowerSources reducing the less lithium manganese phosphate particle of sintering temperature preparation size, 2007,174:949 ~ 953), although the particle size reducing material improves the chemical property of material to a certain extent, but the growth of material crystal formation can be affected simultaneously, cause the crystal structure of material unstable and with impurity, thus affect the cycle performance of material, cannot needs of production be met.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of manganese-lithium phosphate anode material and preparation method thereof, and the manganese-lithium phosphate anode material obtained has good discharge capacity and cycle performance.
The invention provides a kind of manganese-lithium phosphate anode material, comprise lithium manganese phosphate and carbon that molecular formula is formula (I),
LiMn
1-xm
xpO
4(I), wherein, 0≤x≤0.2;
M be selected from Ti, Co, Fe, Mg, Al, Cr, Nb any one;
Described manganese-lithium phosphate anode material is the hollow ball structure that sheet-like particle is formed.
Preferably, the specific area of described manganese-lithium phosphate anode material is 40m
2/ g ~ 100m
2/ g.
Preferably, the mass ratio of described carbon and lithium manganese phosphate is 0.1 ~ 0.3:1.
Present invention also offers the preparation method of described manganese-lithium phosphate anode material, comprise the following steps:
A, by P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant mix, obtain suspension;
Wherein, M is selected from any one in Ti, Co, Fe, Mg, Al, Cr, Nb;
B, by described steps A) suspension that obtains carries out adding thermal response, obtains lithium manganese phosphate precursor powder;
C, by described step B) the lithium manganese phosphate precursor powder that obtains carries out roasting, obtains the manganese-lithium phosphate anode material with hollow ball structure.
Preferably, in described P source compound, manganese source compound, M compound, Li source compound, the mol ratio of P:Mn:M:Li is (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1).
Preferably, the quality of described carbon-source cpd be described P source compound, manganese source compound, doped chemical M compound, Li source compound quality summation 10% ~ 30%; The quality of described surfactant be described P source compound, manganese source compound, doped chemical M compound, Li source compound quality summation 1% ~ 10%.
Preferably, described surfactant is selected from any one or a few in citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, amino acid, Qu Latong, sulfonic acid.
Preferably, described P source compound is selected from any one or a few 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 be selected from manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide any one or a few; Described Li source compound be selected from lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium any one or a few; Described M compound is selected from containing any one or a few in the oxide of M, hydroxide, nitrate, acylate; Described carbon-source cpd be selected from conductive black, carbon nano-tube, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide any one or a few.
Preferably, described step B) in, described in add thermal response temperature be 150 DEG C ~ 250 DEG C, described in add thermal response time be 5h ~ 15h.
Preferably, described step C) in, the temperature of described roasting is 500 DEG C ~ 700 DEG C, and the time of described roasting is 2h ~ 8h.
Manganese-lithium phosphate anode material provided by the invention comprises the lithium manganese phosphate and carbon: LiMn that molecular formula is formula (I)
1-xm
xpO
4(I), wherein, 0≤x≤0.2; M be selected from Ti, Co, Fe, Mg, Al, Cr, Nb any one.Compared with prior art, manganese-lithium phosphate anode material provided by the invention is hollow ball structure, and the structure of its hollow ball is formed by the primary particle of sheet.Wherein, the sheet oriented growth of primary particle can shorten the evolving path of lithium ion in lithium manganese phosphate particle, thus improves diffusion rate; The structure of hollow ball, advantageously in infiltration and the storage of electrolyte and electrode material, makes the deintercalation of lithium ion and transmits more convenient, thus improve discharge capacity and the cycle performance of lithium manganese phosphate material.
The test experiments result of chemical property shows, the manganese-lithium phosphate anode material with hollow ball structure provided by the invention, and at room temperature 0.1C first discharge specific capacity reaches 160mAh/g, and the 1C normal temperature 100 weeks capacity that circulate are unattenuated.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1;
Fig. 3 is the graph of pore diameter distribution of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1;
Fig. 4 is the first discharge specific capacity figure of battery prepared by the embodiment of the present invention and comparative example;
Fig. 5 is the cyclic curve figure of battery prepared by the embodiment of the present invention and comparative example;
Fig. 6 is the first discharge specific capacity figure of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 2;
Fig. 7 is the first discharge specific capacity figure of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 3.
Embodiment
The invention provides a kind of manganese-lithium phosphate anode material, comprise lithium manganese phosphate and carbon that molecular formula is formula (I),
LiMn
1-xm
xpO
4(I), wherein, 0≤x≤0.2;
M be selected from Ti, Co, Fe, Mg, Al, Cr, Nb any one;
Described manganese-lithium phosphate anode material is the hollow ball structure that sheet-like particle is formed.
Compared with prior art, manganese-lithium phosphate anode material provided by the invention is hollow ball structure, and the structure of its hollow ball is formed by the primary particle of sheet.Wherein, the sheet oriented growth of primary particle can shorten the evolving path of lithium ion in lithium manganese phosphate particle, thus improves diffusion rate; The structure of hollow ball, advantageously in infiltration and the storage of electrolyte and electrode material, makes the deintercalation of lithium ion and transmits more convenient, thus improve discharge capacity and the cycle performance of lithium manganese phosphate material.
Manganese-lithium phosphate anode material provided by the invention is hollow ball structure, and its specific area is preferably 40m
2/ g ~ 100m
2/ g, is more preferably 60m
2/ g ~ 80m
2/ g.
Manganese-lithium phosphate anode material provided by the invention contains lithium manganese phosphate and carbon, and the mass ratio of described carbon and lithium manganese phosphate is preferably 0.1 ~ 0.3:1, is more preferably 0.15 ~ 0.25:1.
Present invention also offers the preparation method of above-mentioned manganese-lithium phosphate anode material:
A, by P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant mix, obtain suspension;
Wherein, M is selected from any one in Ti, Co, Fe, Mg, Al, Cr, Nb;
B, by described steps A) suspension that obtains carries out adding thermal response, obtains lithium manganese phosphate precursor powder;
C, by described step B) the lithium manganese phosphate precursor powder that obtains carries out roasting, obtains the manganese-lithium phosphate anode material with hollow ball structure.
The present invention for raw material, prepares manganese-lithium phosphate anode material with P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant.
In the present invention, described P source compound be preferably in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium any one or a few, be more preferably any one or two kinds in phosphoric acid and diammonium hydrogen phosphate.
Described manganese source compound be preferably in manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide any one or a few, be more preferably in manganese carbonate, manganese acetate and manganese dioxide any one or a few.
In described M compound, M be preferably in Ti, Co, Fe, Mg, Al, Cr, Nb any one, be more preferably in Ti, Fe and Mg any one.Described M compound is preferably containing any one or a few in the oxide of M, hydroxide, nitrate, acylate, is more preferably the oxide containing M.
Described Li source compound be preferably in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium any one or a few, be more preferably in lithium hydroxide, lithium carbonate and lithium acetate any one or a few.
Described carbon-source cpd be preferably in conductive black, carbon nano-tube, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide any one or a few, be more preferably in sucrose, glucose and polyvinyl alcohol any one or a few.
Described surfactant be preferably in citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, amino acid, Qu Latong, sulfonic acid any one or a few, be more preferably in softex kw, Qu Latong and citric acid any one or a few.
The source of the present invention to above-mentioned P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant there is no particular/special requirement, can be generally commercially available.
First P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant mix by the present invention, obtain suspension.The solid content of described suspension is preferably 20wt% ~ 40wt%.
In the present invention, in described P source compound, manganese source compound, M compound, Li source compound, the mol ratio of P:Mn:M:Li is preferably (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1), is more preferably (1 ~ 1.08): (0.85 ~ 1): (0.15 ~ 0): (1 ~ 1.08).The Functionality, quality and appealing design of described carbon-source cpd elect as described P source compound, manganese source compound, M compound, Li source compound quality summation 10% ~ 30%, be more preferably 15% ~ 25%.The Functionality, quality and appealing design of described surfactant elect as described P source compound, manganese source compound, M compound, Li source compound quality summation 1% ~ 10%, be more preferably 2% ~ 9%.
After obtaining suspension, described suspension is carried out adding thermal response, obtains lithium manganese phosphate precursor powder.In the present invention, described in add thermal response temperature be preferably 150 DEG C ~ 250 DEG C, be more preferably 180 DEG C ~ 230 DEG C; The described time adding thermal response is 5h ~ 15h, is more preferably 8h ~ 13h.
Obtain lithium manganese phosphate precursor last, carried out roasting, obtain the manganese-lithium phosphate anode material with hollow ball structure.In the present invention, the temperature of described roasting is preferably 500 DEG C ~ 700 DEG C, is more preferably 550 DEG C ~ 680 DEG C.The time of described roasting is preferably 2h ~ 8h, is more preferably 3h ~ 7h.Roasting of the present invention is preferably carried out under nitrogen protection.In roasting process, surfactant ablated fall, thus formed hollow ball structure.
Described manganese-lithium phosphate anode material is the hollow ball formed by the primary particle of sheet, and its specific area is preferably 40m
2/ g ~ 100m
2/ g, is more preferably 60m
2/ g ~ 80m
2/ g.
Carry out electro-chemical test to manganese-lithium phosphate anode material provided by the invention, result shows, its at room temperature 0.1C first discharge specific capacity reach 160mAh/g, and the 1C normal temperature 100 weeks capacity that circulate are unattenuated, have excellent chemical property.
Manganese-lithium phosphate anode material provided by the invention comprises the lithium manganese phosphate and carbon: LiMn that molecular formula is formula (I)
1-xm
xpO
4(I), wherein, 0≤x≤0.2; M be selected from Ti, Co, Fe, Mg, Al, Cr, Nb any one.Compared with prior art, manganese-lithium phosphate anode material provided by the invention is hollow ball structure, and the structure of its hollow ball is formed by the primary particle of sheet.Wherein, the sheet oriented growth of primary particle can shorten the evolving path of lithium ion in lithium manganese phosphate particle, thus improves diffusion rate; The structure of hollow ball, advantageously in infiltration and the storage of electrolyte and electrode material, makes the deintercalation of lithium ion and transmits more convenient, thus improve discharge capacity and the cycle performance of lithium manganese phosphate material.
In order to further illustrate the present invention, below in conjunction with embodiment, manganese phosphate potassium positive electrode provided by the invention and preparation method thereof is described in detail.
Embodiment 1
By the phosphoric acid of 115.3g 85wt%, 93.1g manganese carbonate, 15.17g iron oxide, 46.16g lithium hydroxide, 80.92g sucrose and the mixing of 2.7g softex kw, be scattered in 824.4g deionized water, obtain the suspension that solid content is 30wt%; Then add in reactor by the suspension obtained, be heated to 150 DEG C of reaction 15h in confined conditions, question response completes and after being cooled to room temperature, washs product, filters, dry, obtains lithium manganese phosphate presoma powder; Then the lithium manganese phosphate presoma powder high-temperature roasting 8h under nitrogen protection will obtained, sintering temperature is 500 DEG C, is then cooled to room temperature, obtains the manganese-lithium phosphate anode material with hollow ball structure, and its molecular formula is LiMn
0.81fe
0.19pO
4/ C.
Component and Shape measure are carried out to manganese-lithium phosphate anode material prepared by embodiment 1.Japanese Shimadzu XRD-6000 type x-ray powder diffraction instrument (XRD) is adopted to detect its component, result as shown in Figure 1, Fig. 1 is the X-ray diffractogram of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1, wherein, abscissa is angle 2 θ, and unit is: degree (o); Ordinate is diffracted intensity, and unit is: absolute unit (a.u.).As shown in Figure 1, what show in its X-ray diffraction spectrogram is lithium manganese phosphate characteristic peak (●), not impurity peaks.
Adopt Zeiss, Germany company SUPRA-55 type field emission scanning electron microscope (SEM) to carry out Shape measure to lithium manganese phosphate material prepared by embodiment 1, as shown in Figure 2, Fig. 2 is the scanning electron microscope (SEM) photograph of manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1 to result.As shown in Figure 2, the manganese-lithium phosphate anode material that prepared by the present invention is the hollow ball structure formed by the primary particle of sheet.
Micromeritics Tristar II 3020 v1.03 type analysis instrument is adopted to carry out pore-size distribution test to manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1, test condition is as follows: vacuumize degasification 12 hours at 100 DEG C, pore-size distribution test is carried out under liquid nitrogen temperature (77K), Barrett-Joyner-Halenda (BJH) model is adopted to calculate the pore-size distribution of microballoon, the results are shown in Figure the graph of pore diameter distribution that 3, Fig. 3 is manganese-lithium phosphate anode material prepared by the embodiment of the present invention 1.Adopt Brunauer-Emmett-Teller (BET) method to calculate microballoon specific area, result shows that its specific area is 77.14m
2/ g.
From Fig. 1, Fig. 2 and Fig. 3, manganese-lithium phosphate anode material provided by the invention is the hollow ball structure formed by the primary particle of sheet, has higher purity and larger specific area and less aperture.
Electro-chemical test is carried out to manganese-lithium phosphate anode material prepared by embodiment 1.Lithium manganese phosphate material embodiment 1 prepared mixes by the mass ratio of 90:5:5 with acetylene black conductor and Kynoar binding agent, be applied in aluminum foil current collector, obtaining diameter with sheet-punching machine after 80 DEG C of oven dry is that the electrode slice of 1cm is as positive pole, negative pole is metal lithium sheet, barrier film is Celgard 2400, and electrolyte solution is ethylene carbonate (EC)+dimethyl carbonate (DMC)+methyl ethyl carbonate (EMC)+1mol/L LiPF
6, 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 CR2032 button half-cell.Adopt the blue electric CT 2001A type battery test system in Wuhan to carry out electrochemical property test to CR2032 button half-cell, voltage range is 2.0V ~ 4.5V, and current density converts by 0.1C=17mA/g and 1C=170mA/g, and test result is shown in Fig. 4 and Fig. 5.Fig. 4 is the first discharge specific capacity figure of battery prepared by the embodiment of the present invention and comparative example, and wherein, abscissa is specific discharge capacity, and unit is: MAh/g; Ordinate is voltage, and unit is: volt (Vs.Li/Li
+), curve a is the first discharge specific capacity curve chart of battery prepared by the embodiment of the present invention 1.Fig. 5 is the cyclic curve figure of battery prepared by the embodiment of the present invention and comparative example, and wherein, abscissa is cycle period, and unit is week; Ordinate is specific discharge capacity, and unit is: MAh/g, curve a is the cyclic curve figure of battery prepared by the embodiment of the present invention 1.From Fig. 4 and Fig. 5, the manganese-lithium phosphate anode material with hollow ball structure prepared of the embodiment of the present invention 1 at room temperature 0.1C first discharge specific capacity reaches 160mAh/g, and the 1C normal temperature 100 weeks capacity that circulate are unattenuated.
Comparative example 1
By the phosphoric acid of 115.3g 85wt%, 93.1g manganese carbonate, 15.17g iron oxide, 46.16g lithium hydroxide and the mixing of 80.92g sucrose, be scattered in 824g deionized water, obtain the suspension that solid content is 30wt%; Then add in reactor by the suspension obtained, be heated to 150 DEG C of reaction 15h in confined conditions, question response completes and after being cooled to room temperature, washs product, filters, dry, obtains lithium manganese phosphate presoma powder; Then the lithium manganese phosphate presoma powder high-temperature roasting 8h under nitrogen protection will obtained, sintering temperature is 500 DEG C, is then cooled to room temperature, obtains manganese-lithium phosphate anode material, and its molecular formula is LiMn
0.81fe
0.19pO
4/ C.
Electro-chemical test is carried out to lithium manganese phosphate material prepared by comparative example 1.The lithium manganese phosphate material prepared by comparative example 1 mixes by the mass ratio of 90:5:5 with acetylene black conductor and Kynoar binding agent, be applied in aluminum foil current collector, obtaining diameter with sheet-punching machine after 80 DEG C of oven dry is that the electrode slice of 1cm is as positive pole, negative pole is metal lithium sheet, barrier film is Celgard 2400, and electrolyte solution is EC+ dimethyl carbonate (DMC)+EMC+1mol/L LiPF
6, 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 CR2032 button half-cell.Adopt the blue electric CT 2001A type battery test system in Wuhan to carry out electrochemical property test to CR2032 button half-cell, voltage range is 2.0V ~ 4.5V, and current density converts by 0.1C=17mA/g and 1C=170mA/g, and test result is shown in Fig. 4 and Fig. 5.Fig. 4 is the first discharge specific capacity figure of battery prepared by the embodiment of the present invention and comparative example, and wherein, abscissa is specific discharge capacity, and unit is: MAh/g; Ordinate is voltage, and unit is: volt (Vs.Li/Li
+), curve b is the first discharge specific capacity curve chart of the battery of comparative example 1 of the present invention preparation.Fig. 5 is the cyclic curve figure of battery prepared by the embodiment of the present invention and comparative example, and wherein, abscissa is cycle period, and unit is week; Ordinate is specific discharge capacity, and unit is: MAh/g, curve b is the cyclic curve figure of the battery of comparative example 1 of the present invention preparation.
Through more known, the manganese-lithium phosphate anode material with hollow ball structure provided by the invention, has higher specific discharge capacity, better cycle performance.
Embodiment 2
By 138.66g diammonium hydrogen phosphate, 220.58g manganese acetate, the titanium dioxide of 7.98,38.79g lithium carbonate, 40.6g sucrose and 20.3g song draw logical mixing, are scattered in 700g deionized water, obtain the suspension that solid content is 40%; Then add in reactor by the suspension obtained, be heated to 200 DEG C of reaction 10h in confined conditions, question response completes and after being cooled to room temperature, washs product, filters, dry, obtains lithium manganese phosphate presoma powder; Then the lithium manganese phosphate presoma powder high-temperature roasting 5h under nitrogen atmosphere protection will obtained, sintering temperature is 600 DEG C, is then cooled to room temperature, obtains the manganese-lithium phosphate anode material with hollow ball structure, and its molecular formula is LiMn
0.9ti
0.1pO
4/ C.
According to the detection method of embodiment 1, X-ray diffraction analysis and ESEM detection are carried out to manganese-lithium phosphate anode material prepared by embodiment 2, result shows the manganese-lithium phosphate anode material that can be prepared the hollow ball structure formed by the primary particle of sheet by the method, and the manganese-lithium phosphate anode material prepared has higher purity.Carry out specific area detection to it, result shows that its specific area is 78.23m
2/ g.Carry out pore-size distribution detection to it, result shows that it has less aperture.
Electro-chemical test is carried out to manganese-lithium phosphate anode material prepared by the embodiment of the present invention 2, the results are shown in Figure the first discharge specific capacity figure that 6, Fig. 6 is manganese-lithium phosphate anode material prepared by the embodiment of the present invention 2.As shown in Figure 6, the embodiment of the present invention 2 prepare the manganese-lithium phosphate anode material with hollow ball structure at room temperature 0.1C first discharge specific capacity reach 160mAh/g.
Embodiment 3
By 126.53g diammonium hydrogen phosphate, 86.07g manganese dioxide, 0.4g magnesium oxide, 65.99g lithium acetate, 55.80g polyvinyl alcohol and the mixing of 27.8g citric acid, be scattered in 1160g deionized water, obtain the suspension that solid content is 20%; Then add in reactor by the suspension obtained, be heated to 250 DEG C of reaction 5h in confined conditions, question response completes and after being cooled to room temperature, washs product, filters, dry, obtains lithium manganese phosphate presoma powder; Then the lithium manganese phosphate presoma powder high-temperature roasting 2h under nitrogen atmosphere protection will obtained again, sintering temperature is 700 DEG C, is then cooled to room temperature, obtains the manganese-lithium phosphate anode material with hollow ball structure, and its molecular formula is LiMn
0.99mg
0.01pO
4/ C.
According to the detection method of embodiment 1, X-ray diffraction analysis and ESEM detection are carried out to manganese-lithium phosphate anode material prepared by embodiment 3, result shows the manganese-lithium phosphate anode material that can be prepared the hollow ball structure formed by the primary particle of sheet by the method, and the manganese-lithium phosphate anode material prepared has higher purity.Carry out specific area detection to it, result shows that its specific area is 76.14m
2/ g.Carry out pore-size distribution detection to it, result shows that it has less aperture.
Electro-chemical test is carried out to manganese-lithium phosphate anode material prepared by the embodiment of the present invention 3, the results are shown in Figure the first discharge specific capacity figure that 7, Fig. 7 is manganese-lithium phosphate anode material prepared by the embodiment of the present invention 3.As shown in Figure 7, the embodiment of the present invention 3 prepare the manganese-lithium phosphate anode material with hollow ball structure at room temperature 0.1C first discharge specific capacity reach 160mAh/g.
From above-described embodiment and comparative example, manganese-lithium phosphate anode material provided by the invention, the hollow ball structure that the primary particle for sheet is formed, has good discharge capacity and cycle performance.
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 (8)
1. a manganese-lithium phosphate anode material, is characterized in that, comprises lithium manganese phosphate and carbon that molecular formula is formula (I),
LiMn
1-xm
xpO
4(I), wherein, 0≤x≤0.2;
M be selected from Ti, Co, Fe, Mg, Al, Cr, Nb any one;
Described manganese-lithium phosphate anode material is the hollow ball structure that sheet-like particle is formed;
The specific area of described positive electrode is 60m
2/ g ~ 80m
2/ g.
2. manganese-lithium phosphate anode material according to claim 1, is characterized in that, the mass ratio of described carbon and lithium manganese phosphate is 0.1 ~ 0.3:1.
3. a preparation method for manganese-lithium phosphate anode material according to claim 1, is characterized in that, comprises the following steps:
A, by P source compound, manganese source compound, M compound, Li source compound, carbon-source cpd and surfactant mix, obtain suspension;
Wherein, M is selected from any one in Ti, Co, Fe, Mg, Al, Cr, Nb;
B, by described steps A) suspension that obtains carries out adding thermal response, obtains lithium manganese phosphate precursor powder;
Described step B) in, described in add thermal response temperature be 150 DEG C ~ 250 DEG C, described in add thermal response time be 5h ~ 15h;
C, by described step B) the lithium manganese phosphate precursor powder that obtains carries out roasting, obtains the manganese-lithium phosphate anode material with hollow ball structure.
4. preparation method according to claim 3, it is characterized in that, in described P source compound, manganese source compound, M compound, Li source compound, the mol ratio of P:Mn:M:Li is (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1).
5. preparation method according to claim 3, is characterized in that, the quality of described carbon-source cpd be described P source compound, manganese source compound, doped chemical M compound, Li source compound quality summation 10% ~ 30%; The quality of described surfactant be described P source compound, manganese source compound, doped chemical M compound, Li source compound quality summation 1% ~ 10%.
6. preparation method according to claim 3, is characterized in that, described surfactant be selected from citric acid, ascorbic acid, stearic acid, oleic acid, softex kw, amino acid, Qu Latong, sulfonic acid any one or a few.
7. preparation method according to claim 3, is characterized in that, described P source compound be selected from phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium any one or a few; Described manganese source compound be selected from manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and manganous hydroxide any one or a few; Described Li source compound be selected from lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithium any one or a few; Described M compound is selected from containing any one or a few in the oxide of M, hydroxide, nitrate, acylate; Described carbon-source cpd be selected from conductive black, carbon nano-tube, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose and polysaccharide any one or a few.
8. preparation method according to claim 3, is characterized in that, described step C) in, the temperature of described roasting is 500 DEG C ~ 700 DEG C, and the time of described roasting is 2h ~ 8h.
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| CN104733730B (en) * | 2015-03-24 | 2017-10-03 | 中国科学院宁波材料技术与工程研究所 | A kind of anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| 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 |
| CN107628594B (en) * | 2017-08-22 | 2020-01-07 | 西安建筑科技大学 | Solvothermal preparation method of 3D flower-shaped lithium iron phosphate cathode material assembled by two-dimensional nanosheets |
| 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 |
| CN111180688B (en) * | 2019-12-30 | 2022-08-05 | 中南大学 | Micron-scale hollow porous sodium-ion battery positive electrode material and preparation method thereof |
| 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 |
| CN114142026B (en) * | 2021-12-02 | 2023-10-20 | 河南师范大学 | Manganese-based polyanion positive electrode material, preparation method thereof and sodium ion battery |
| CN115448284B (en) * | 2022-09-30 | 2024-01-30 | 曲靖市德方纳米科技有限公司 | Method for preparing battery-grade lithium manganese phosphate composite material by using minerals and application of battery-grade lithium manganese phosphate composite material |
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