CN102983334A - Positive pole material of lithium ion battery and preparation method of material - Google Patents
Positive pole material of lithium ion battery and preparation method of material Download PDFInfo
- Publication number
- CN102983334A CN102983334A CN201210551815XA CN201210551815A CN102983334A CN 102983334 A CN102983334 A CN 102983334A CN 201210551815X A CN201210551815X A CN 201210551815XA CN 201210551815 A CN201210551815 A CN 201210551815A CN 102983334 A CN102983334 A CN 102983334A
- Authority
- CN
- China
- Prior art keywords
- lithium
- manganese
- compound
- source compound
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a positive pole material of a lithium ion battery. The positive pole material of the lithium ion battery comprises a plurality of sheet-like carbon composite manganese-lithium phosphate material sheets; and the sheet-like carbon composite manganese-lithium phosphate material sheets are arranged in a radial shape. The manganese-lithium phosphate has a chemical formula shown by the formula (1): LiMn1-xMxPO4 (I), wherein x is more than 0 and is less than 0.2; and M is one of Ti, Co, Fe, Mg, Al, Cr and Nb. The positive pole material of the lithium ion battery provided by the invention comprises the sheet-like carbon composite manganese-lithium phosphate material sheets; the sheet-like carbon composite manganese-lithium phosphate material sheets are arranged in the radial shape to form multiple turns, so that the diffusion path of lithium ions in manganese-lithium phosphate grains can be reduced by using the positive pole material with the shape; and meanwhile, the positive pole material with the shape has a specific surface area, so that lithium ions are rapidly deintercalated and transferred. Furthermore, the positive pole material and a battery conduction additive are sufficiently and uniformly mixed, so that the positive pole material of the lithium ion battery provided by the invention has high discharge capability and circulation property.
Description
Technical field
The present invention relates to the lithium ion battery electrode material technical field, relate in particular 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 studies show that, the phosphate system material of olivine-type structure is as the positive electrode of lithium ion battery, this obviously is better than traditional layer structure material on aspect two in security performance and cycle life, such as cobalt acid lithium, lithium nickelate and ternary material etc., its representative materials LiFePO4 (LiFePO
4) confirmed by academia and industrial circle broad research, and be widely used in the fields such as electrokinetic cell and energy-storage battery.But the voltage platform of lithium metal 3.4V defines the lifting of LiFePO4 energy density relatively, thereby 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, lithium manganese phosphate can improve 0.7V with current potential, and it also has the theoretical specific capacity of 171mAh/g, so that it is expected to become the positive electrode of lithium ion battery with high energy density of new generation.But the electronic conductivity of lithium manganese phosphate material and lithium ion diffusion rate are lower than LiFePO4, so the lithium manganese phosphate material of non-modified can't satisfy the practical application needs at all.
For electronic conductivity and the lithium ion diffusion rate that improves manganese-lithium phosphate anode material, prior art is mainly come manganese-lithium phosphate anode material is carried out modification by carbon coating, doped with metal elements and material granule nanometer, thereby improves the chemical property of lithium manganese phosphate material.40520 ~ 4057.) etc. Huihua Yi(Electrochimica Acta, 2011,56 (11): the people adopts solid phase method to synthesize manganese-lithium phosphate anode material, with 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 of 14wt.% mixes, then under the argon gas atmosphere protection, 800 ℃ of high-temperature calcination 10h, obtaining chemical composition is LiMn
0.9Fe
0.05Mg
0.05PO
4The material of/C, the first discharge capacity that gets 0.1C through electrochemical property test is 140mAh/g.This solid phase method technique is simple, and suitability for industrialized production is convenient, and is large but the prepared material of the method still exists particle, and particle diameter heterogeneity and carbon coat the problems such as imperfect, and this will have a strong impact on the cycle performance of material, the performances such as high rate performance and high low temperature.In order to control the granular size of positive electrode, Thierry Drezen(Journal of Power Sources, 2007,949 ~ 953.) etc. 174 (2): the people is by adopting sol-gal process and regulation and control sintering temperature to control the material granule particle diameter, first lithium acetate, manganese acetate and ammonium dihydrogen phosphate are dissolved in the deionized water, then to wherein adding the chelating agent glycolic, between 60 ℃ ~ 75 ℃, obtain gel, then obtain LiMnPO at the lower calcining 3h of different temperature (400 ℃ ~ 800 ℃)
4Material.Characterize through ESEM, the material particle size minimum for preparing 520 ℃ of calcinings 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, and can control the particle diameter of material, this low-temperature bake is processed and can be reduced the crystallinity of material, thereby 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 is radial arrangement; Described lithium manganese phosphate has chemical formula shown in the formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0＜x＜0.2;
M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.
Preferably, 0.01≤x≤0.19.
Preferably, described M is a kind of among Ti, Fe, Mg, Al and the 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, may further comprise the steps:
With P source compound, manganese source compound, contain M compound, Li source compound, carbon-source cpd and surfactant and in water, mix, obtain suspension, described M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb;
In confined conditions, described suspension is heated, obtain the positive electrode presoma;
In inert atmosphere, described positive electrode presoma is carried out roasting, obtain 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 lithiums;
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 the manganous hydroxide;
In the oxide that the described M of containing compound is M, hydroxide, nitrate, the acylate one or more;
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 lithiums;
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 the 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 the sulfonic acid.
Preferably, described P source compound, manganese source compound, the mol ratio that contains phosphorus, manganese, M and Li in M compound, the Li source compound are (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1);
The quality of described carbon-source cpd is P source compound, manganese source compound, contain the 5wt% ~ 15wt% of M compound and Li source compound gross mass;
The quality of described surfactant is P source compound, manganese source compound, contain the 1wt% ~ 10wt% of 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 ℃ ~ 250 ℃;
The time of described heating is 5h ~ 15h.
Preferably, the temperature of described roasting is 500 ℃ ~ 700 ℃;
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 is radial arrangement; Described lithium manganese phosphate has chemical formula: LiMn shown in the formula (I)
1-xM
xPO
4(I); Wherein, 0＜x＜0.2; M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.Anode material for lithium-ion batteries provided by the invention is comprised of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium is radial arrangement, such oriented growth has shortened the evolving path of lithium ion in the lithium manganese phosphate particle, has improved the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition has increased the specific area of material simultaneously, thereby enlarged contacting and wetted area of positive electrode and electrolyte, make lithium ion take off embedding and transmit rapider, and so that positive electrode is more abundant and even with mixing of battery conductive additive, improved further the conductance of positive electrode, thereby 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 that the first discharge capacity of anode material for lithium-ion batteries provided by the invention can reach 160mAh/g.
Description of drawings
Fig. 1 is the XRD spectra of the positive electrode that obtains of the embodiment of the invention 1;
Fig. 2 is that the positive electrode that the embodiment of the invention 1 obtains amplifies 10.0k stereoscan photograph doubly;
Fig. 3 is that the positive electrode that the embodiment of the invention 1 obtains amplifies 50.0k stereoscan photograph doubly;
Fig. 4 is that the positive electrode that the embodiment of the invention 1 obtains is the transmission electron microscope photo of 5.6mm at WD;
Fig. 5 is that the positive electrode that the embodiment of the invention 1 obtains is the projection electromicroscopic photograph of 4.6mm at WD;
Fig. 6 is the positive electrode first discharge specific capacity curve that the embodiment of the invention 1 and comparative example 1 obtain;
Fig. 7 is the first discharge specific capacity curve of the positive electrode that obtains of the embodiment of the invention 2;
Fig. 8 is the positive electrode first discharge specific capacity curve that the embodiment of the invention 3 obtains.
Embodiment
The invention provides a kind of anode material for lithium-ion batteries, comprise that multi-disc sheet carbon compound phosphoric acid manganese lithium material forms, described multi-disc sheet carbon compound phosphoric acid manganese lithium material is radial arrangement; Described lithium manganese phosphate has chemical formula shown in the formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0＜x＜0.2;
M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the 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 are radial oriented growth, obtain having the anode material for lithium-ion batteries of the 3-D solid structure of globoid or spheroid form.In the present invention, described each sheet is radial arrangement, can be irregular radial arrangement, preferred each sheet sheet carbon compound phosphoric acid manganese lithium material interlocks but nonoverlapping arrangement, the present invention does not get rid of yet has sheet carbon compound phosphoric acid manganese lithium material stretcher to be on the carbon compound phosphoric acid manganese lithium material of radial arrangement in multi-disc, participate in the stereoscan photograph of positive electrode shown in Figure 2, anode material for lithium-ion batteries provided by the invention such as corolla shape, 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 has shortened the evolving path of lithium ion in the lithium manganese phosphate particle, has improved the conductivity of positive electrode; And be radial staggered but not the structure of overlapping arrangement increased the specific area of positive electrode, thereby enlarged contacting and infiltration of positive electrode and electrolyte, so that lithium ion takes off embedding and transmits rapider, so that positive electrode is more all even abundant with mixing of battery conductive agent, improved the conductivity of positive electrode, thereby so that 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, and more preferably 20nm ~ 250nm most preferably is 30nm ~ 200nm;
In the present invention, described lithium manganese phosphate has chemical formula shown in the formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0＜x＜0.2, preferred 0.01≤x≤0.19;
M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb, is preferably among Ti, Fe, Mg, Al and the Cr a kind of, more preferably a kind of among Ti, Fe and the Mg.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
With P source compound, manganese source compound, contain M compound, Li source compound, carbon-source cpd and surfactant and in water, mix, obtain suspension, described M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb;
In confined conditions, described suspension is heated, obtain the positive electrode presoma;
In inert atmosphere, described positive electrode presoma is carried out roasting, obtain anode material for lithium-ion batteries.
The present invention take P source compound, manganese source compound, contain M compound, Li source compound, carbon-source cpd and surfactant as raw material, heat first reaction after it is mixed, obtain the positive electrode presoma; Again the positive electrode presoma that obtains is carried out roasting, obtain anode material for lithium-ion batteries.The present invention is with the raw material of surfactant as the preparation positive electrode, surfactant can be regulated the direction of growth and the structure thereof of positive electrode, make the compound lithium manganese phosphate of carbon be radial growth, one end of the sheet carbon compound phosphoric acid manganese lithium that obtains links together, carbon compound phosphoric acid manganese lithium is radial oriented growth centered by its end that links together, shortened the evolving path of lithium ion in the lithium manganese phosphate particle, and the positive electrode that obtains has larger specific area, improved the conductivity of material, thereby made the positive electrode that obtains have higher discharge capacity and cycle performance.
The present invention at first with P source compound, manganese source compound, contain M compound, Li source compound, carbon-source cpd and surfactant and in water, mix, obtain suspension, described M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.The present invention does not have special restriction to P source compound, manganese source compound, the order by merging that contains 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 to get final product;
In the present invention, described P source compound is preferably one or more in phosphoric acid or the phosphate, one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums more preferably, most preferably be one or more in phosphoric acid, diammonium hydrogen phosphate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums, the most be preferably in phosphoric acid and the diammonium hydrogen phosphate one or both;
Described manganese source compound is preferably one or more in the hydroxide of the oxide of manganese salt, manganese and manganese, one or more in manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese carbonate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide and the manganous hydroxide more preferably, most preferably be in manganese carbonate, manganese acetate, manganese dioxide, the manganous hydroxide one or more, the most be preferably in manganese carbonate, manganese acetate and the manganese dioxide one or more;
Described M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb, is preferably among Ti, Fe, Mg, Al and the Cr a kind of, more preferably a kind of among Ti, Fe and the Mg; The described M of containing compound is preferably one or more in the oxide, hydroxide, nitrate, acylate of M, the more preferably oxide of M;
Described Li source compound is preferably one or more in the hydroxide of lithium salts and lithium, one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate and phosphoric acid hydrogen two lithiums more preferably, most preferably be in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and the lithium phosphate one or more, the most be preferably in lithium hydroxide, lithium carbonate and the 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 the polysaccharide, one or more in carbon nano-tube, acetylene black, sucrose, polyvinyl alcohol, polysaccharide and the phenolic resins more preferably most preferably are in carbon nano-tube, sucrose and the polyvinyl alcohol one or more;
Described surfactant can be anion surfactant, also can be cationic surfactant, can also be zwitterionic surfactant, 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, in Qu Latong and the sulfonic acid one or more, stearic acid more preferably, hexadecane and trimethylammonium bromide, neopelex, among amino acid and the Qu Latong one or more most preferably are Qu Latong, in hexadecane and trimethylammonium bromide and the neopelex one or more;
In the present invention, described P source compound, manganese source compound, the mol ratio that contains phosphorus, manganese, M and lithium in M compound, the Li source compound are preferably (0.8 ~ 1.5): (0.5 ~ 1.5): (0.5 ~ 0): (0.5 ~ 1.5), the described M of containing compound is not 0, more preferably (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0.01): (1 ~ 1.1); The quality optimization of described carbon-source cpd is P source compound, manganese source compound, contain the 5wt%15wt% of M compound and Li source compound gross mass, more preferably 8wt% ~ 12wt%; The quality optimization of described surfactant is P source compound, manganese source compound, contain the 1wt% ~ 10wt% of M compound and Li source compound gross mass, more preferably 3wt% ~ 8wt%;
In the present invention, the solid content of described suspension is preferably 10wt% ~ 50wt%, and more preferably 15wt% ~ 45wt% most preferably is 20wt% ~ 40wt%.
After obtaining suspension, the present invention heats described suspension in confined conditions, obtains the positive electrode presoma.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 to get final product, and places airtight reactor to react such as the suspension that technique scheme can be obtained; In the present invention, the temperature of described heating is preferably 120 ℃ ~ 280 ℃, more preferably 130 ℃ ~ 260 ℃, most preferably is 150 ℃ ~ 150 ℃; The time of described heating is preferably 3h ~ 20h, and more preferably 4h ~ 18h most preferably is 5h ~ 15h.
After finishing the heating to suspension, the present invention preferably is cooled to room temperature with reaction system, then the solid that obtains is washed, filters and drying, obtains the positive electrode presoma.The present invention does not have special restriction to described washing, filtration and dry method, adopts washing well known to those skilled in the art, filtration and dry technical scheme to get final product.
After obtaining the positive electrode presoma, the present invention carries out roasting with described positive electrode presoma in inert gas atmosphere, obtain anode material for lithium-ion batteries.The present invention does not have special restriction to described inert gas, adopts inert gas well known to those skilled in the art to get final product, and inert gas can be nitrogen as described, can be helium yet; The present invention preferably carries out roasting under nitrogen atmosphere; The temperature of described roasting is preferably 450 ℃ ~ 750 ℃, and more preferably 480 ℃ ~ 720 ℃, more preferably 500 ℃ ~ 700 ℃; The time of described roasting is preferably 2h ~ 10h, more preferably 2h ~ 8h.
The present invention preferably is cooled to room temperature with reaction system after finishing roasting to the positive electrode presoma, obtains anode material for lithium-ion batteries.
The present invention forms sign with pattern to the positive electrode that obtains, and detailed process is as follows:
The model that adopts 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, the result shows, do not have impurity peaks in the XRD spectra that obtains, the characteristic peak that only has 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 to anode material for lithium-ion batteries provided by the invention sign, the result shows, positive electrode provided by the invention is to be the radial spheroid that consists of by the multi-disc laminated structure, and an end of described laminated structure links together as the center of spheroid;
The model that the present invention adopts U.S. Merck ﹠ Co., Inc 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 the result shows that the specific area of positive electrode provided by the invention can reach 45.6m
2/ g.
The present invention obtains lithium ion battery with the positive electrode combination that obtains, and has investigated the electric property of the positive electrode that obtains, and detailed process is as follows:
Anode material for lithium-ion batteries provided by the invention is mixed with acetylene black conductor and the Kynoar binding agent mass ratio by 90:5:5 respectively, the mixture that obtains is applied on the aluminum foil current collector, makes the electrode slice that diameter is 1cm with sheet-punching machine after 80 ℃ of oven dry; As positive pole, negative pole is metal lithium sheet with the electrode slice that obtains, and barrier film is Celgard2400, and electrolyte solution is that EC, DMC, EMC and molar concentration are 1mol/L LiPF
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 the blue electric company in Wuhan 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, the 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 is radial arrangement; Described lithium manganese phosphate has chemical formula: LiMn shown in the formula (I)
1-xM
xPO
4(I); Wherein, 0＜x＜0.2; M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.Anode material for lithium-ion batteries provided by the invention is comprised of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium is radial arrangement, such oriented growth has shortened the evolving path of lithium ion in the lithium manganese phosphate particle, has improved the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition has increased the specific area of material simultaneously, thereby enlarged contacting and wetted area of positive electrode and electrolyte, make lithium ion take off embedding and transmit rapider, and so that positive electrode is more abundant and even with mixing of battery conductive additive, improved further the conductance of positive electrode, thereby 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 specify 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 restriction to protection range of the present invention.
In following embodiment, the model that adopts Japanese Shimadzu to produce is that the x-ray powder diffraction instrument (XRD) of XRD-6000 characterizes the composition of anode material for lithium-ion batteries provided by the invention; The model that adopts HIT to produce is the field emission scanning electron microscope (SEM) of S-4800 carries out pattern to anode material for lithium-ion batteries provided by the invention sign; The model that adopts U.S. Merck ﹠ Co., Inc to produce is that the specific surface measuring and analysing meter of ASAP-2020M characterizes the specific area of anode material for lithium-ion batteries provided by the invention; The model that adopts the blue electric company in Wuhan 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 that 85% phosphoric acid, the manganese carbonate of 93.1g, the iron oxide of 15.17g, the lithium hydroxide of 46.16g, sucrose and the 2.7g neopelex of 40.46g are scattered in the deionized water of 730g with the mass concentration of 115.3g, be made into solid content and be 30% suspension; Then above-mentioned suspension is added in the reactor, is heated in confined conditions 200 ℃ of reaction 15h, after question response is finished and is cooled to room temperature, the solid that obtains washed, filters and drying after obtain the manganese phosphate lithium front body powder; With the manganese phosphate lithium front body powder high-temperature roasting 8h under the nitrogen atmosphere protection that obtains, sintering temperature is 500 ℃, then is cooled to room temperature and gets anode material for lithium-ion batteries again.
The present invention carries out the X-ray diffraction analysis with the anode material for lithium-ion batteries that obtains, the result as shown in Figure 1, Fig. 1 is the XRD spectra of the positive electrode that obtains of the embodiment of the invention 1, as seen from Figure 1, the positive electrode that 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 present invention carries out the ESEM scanning analysis with the anode material for lithium-ion batteries that obtains, the result as shown in Figures 2 and 3, Fig. 2 is that the positive electrode that the embodiment of the invention 1 obtains amplifies 10.0k stereoscan photograph doubly, Fig. 3 is that the positive electrode that the embodiment of the invention 1 obtains amplifies 50.0k stereoscan photograph doubly, can be found out by Fig. 2 and Fig. 3, the anode material for lithium-ion batteries that the present invention prepares comprises the multi-disc laminated structure, all laminated structures surround spheroid, these lamellar structures are radial cross laminates arranges, and obtains having the anode material for lithium-ion batteries such as the 3-D solid structure of corolla shape globoid;
The present invention carries out the transmission electron microscope scanning analysis with the anode material for lithium-ion batteries that obtains, the result as shown in Figure 4 and Figure 5, Fig. 4 is that the positive electrode that the embodiment of the invention 1 obtains is the transmission electron microscope photo of 5.6mm at WD, Fig. 5 is that the positive electrode that the embodiment of the invention 1 obtains is the projection electromicroscopic photograph of 4.6mm at WD, can be found out by Fig. 4 and Fig. 5, the positive electrode that the present invention obtains is radial cross arrangement by the multi-disc flaky material and obtains, and the thickness that obtains flaky material is 58.05nm;
The specific area that the present invention detects the anode material for lithium-ion batteries that obtains the present embodiment preparation is 45.6m
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 that present embodiment is obtained mixes by the 90:5:5 mass ratio with acetylene black conductor and Kynoar binding agent respectively, is applied on the aluminum foil current collector, makes the electrode slice that diameter is 1cm with sheet-punching machine after 80 ℃ of oven dry; As positive pole, negative pole is metal lithium sheet with this electrode slice, and barrier film is Celgard2400, and electrolyte solution is that EC, DMC, EMC and molar concentration are the LiPF of 1mol/L
6Mixed solution is at the German Braun UNlab of company 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 that CR2032 button half-cell is carried out electrochemical property test, 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 invention 1 and comparative example 1 obtain, wherein, curve a is the first discharge specific capacity curve of the positive electrode that obtains of the embodiment of the invention 1, can be found out by 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, have higher discharge capacity, obviously be better than the prepared positive electrode of comparative example 1.
Comparative example 1
Be that 85% phosphoric acid, the manganese carbonate of 93.1g, the iron oxide of 15.17g, the lithium hydroxide of 46.16g and the sucrose of 40.46g are scattered in the deionized water of 728g with the 115.3g mass concentration, be made into solid content and be 30% suspension; Then above-mentioned suspension is added in the reactor, be heated in confined conditions 200 ℃ of reaction 15h, after question response is finished and is cooled to room temperature, the solid that obtains is washed, filters and drying, obtain the manganese phosphate lithium front body powder; Then again with the manganese phosphate lithium front body powder high-temperature roasting 8h under the nitrogen atmosphere protection that obtains, sintering temperature is 500 ℃, then is cooled to room temperature and gets anode material for lithium-ion batteries.
The present invention carries out XRD analysis with the anode material for lithium-ion batteries that obtains, and the result shows that 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 present invention carries out the SEM scanning analysis with the anode material for lithium-ion batteries that obtains, and the result shows that the positive electrode that this comparative example obtains is graininess;
The present invention is according to the chemical property of embodiment 1 described technical scheme detection anode material for lithium-ion batteries, and test result as shown in Figure 6.Fig. 6 is the positive electrode first discharge specific capacity curve that the embodiment of the invention 1 and comparative example 1 obtain, wherein, curve b is the first discharge specific capacity curve of the positive electrode that obtains of comparative example 1 of the present invention, by being compared example, curve a and curve b can find out that anode material for lithium-ion batteries provided by the invention has higher discharge capacity.
Embodiment 2
The manganese acetate of the diammonium hydrogen phosphate of 138.66g, 220.58g, the titanium dioxide of 7.98g, the lithium carbonate of 38.79g, sucrose and the 20.3g song of 20.3g are drawn logical being scattered in the deionized water of 670g, be made into solid content and be 40% suspension; Then above-mentioned suspension is added in the reactor, be heated in confined conditions 150 ℃ of reaction 10h, after question response is finished and is cooled to room temperature, the solid that obtains is washed, filters and drying, obtain the manganese phosphate lithium front body powder; Then again with the manganese phosphate lithium front body powder high-temperature roasting 5h under the nitrogen atmosphere protection that obtains, sintering temperature is 600 ℃, then is cooled to room temperature and gets anode material for lithium-ion batteries.
The present invention carries out XRD analysis with the positive electrode that obtains, and the result shows that the positive electrode that the embodiment of the invention 2 obtains is carbon compound phosphoric acid manganese lithium, and its molecular formula is LiMn
0.9Ti
0.1PO
4-C;
The present invention carries out the SEM scanning analysis with the positive electrode that obtains, the result shows, the positive electrode that the present invention makes comprises multi-disc sheet carbon compound phosphoric acid manganese lithium, all sheet carbon compound phosphoric acid manganese lithiums form sphere structure, these sheet carbon compound phosphoric acid manganese lithiums are radial cross laminates to be arranged, and obtains the anode material for lithium-ion batteries with 3-D solid structure such as corolla shape globoid;
The present invention carries out the TEM scanning analysis with the positive electrode that obtains, and the result shows that the thickness of sheet carbon compound phosphoric acid manganese lithium is 100nm in the positive electrode that present embodiment obtains;
The present invention detects the chemical property that obtains anode material for lithium-ion batteries according to embodiment 1 described technical scheme, the result as shown in Figure 7, Fig. 7 is the positive electrode first discharge specific capacity curve that the embodiment of the 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 diammonium hydrogen phosphate of 126.53g, the manganese dioxide of 86.07g, the magnesium oxide of 0.4g, the lithium acetate of 65.99g, polyvinyl alcohol and the 27.8g softex kw of 27.9g are scattered in the deionized water of 1336g, are made into solid content and are 20% suspension; Then above-mentioned suspension is added in the reactor, be heated in confined conditions 250 ℃ of reaction 5h, after question response is finished and is cooled to room temperature, the solid that obtains is washed, filters and drying, obtain the manganese phosphate lithium front body powder; Then again with the manganese phosphate lithium front body powder high-temperature roasting 2h under the nitrogen atmosphere protection that obtains, sintering temperature is 700 ℃, then is cooled to room temperature and obtains anode material for lithium-ion batteries.
The present invention carries out XRD analysis with the positive electrode that obtains, and the result shows that the positive electrode that the embodiment of the invention 2 obtains is carbon compound phosphoric acid manganese lithium, and its molecular formula is LiMn
0.99Mg
0.01PO
4-C;
The present invention carries out the SEM scanning analysis with the positive electrode that obtains, the result shows, the positive electrode that the present invention makes comprises multi-disc sheet carbon compound phosphoric acid manganese lithium, all sheet lithium manganese phosphates form sphere structure, these sheet carbon compound phosphoric acid manganese lithiums are radial cross laminates to be arranged, and obtains the anode material for lithium-ion batteries with 3-D solid structure such as corolla shape globoid;
The present invention carries out the TEM scanning analysis with the positive electrode that obtains, and the result shows that the thickness of sheet carbon compound phosphoric acid manganese lithium is 150nm in the positive electrode that present embodiment obtains;
The present invention detects the chemical property that obtains anode material for lithium-ion batteries according to embodiment 1 described technical scheme, the result as shown in Figure 8, Fig. 8 is the positive electrode first discharge specific capacity curve that the embodiment of the 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 is radial arrangement; Described lithium manganese phosphate has chemical formula: LiMn shown in the formula (I)
1-xM
xPO
4(I); Wherein, 0＜x＜0.2; M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.Anode material for lithium-ion batteries provided by the invention is comprised of the carbon compound phosphoric acid manganese lithium of sheet, described multi-disc sheet carbon compound phosphoric acid manganese lithium is radial arrangement, such oriented growth has shortened the evolving path of lithium ion in the lithium manganese phosphate particle, has improved the conductance of positive electrode; The pattern of the 3-D solid structure of sheet carbon compound phosphoric acid manganese lithium composition has increased the specific area of material simultaneously, thereby enlarged contacting and wetted area of positive electrode and electrolyte, make lithium ion take off embedding and transmit rapider, and so that positive electrode is more abundant and even with mixing of battery conductive additive, improved further the conductance of positive electrode, thereby 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 only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (11)
1. an 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 is radial arrangement; Described lithium manganese phosphate has chemical formula shown in the formula (I):
LiMn
1-xM
xPO
4（I）；
Wherein, 0＜x＜0.2;
M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb.
2. anode material for lithium-ion batteries according to claim 1 is characterized in that, 0.01≤x≤0.19.
3. anode material for lithium-ion batteries according to claim 1 is characterized in that, described M is a kind of among Ti, Fe, Mg, Al and the Cr.
4. anode material for lithium-ion batteries 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. the preparation method of an anode material for lithium-ion batteries may further comprise the steps:
With P source compound, manganese source compound, contain M compound, Li source compound, carbon-source cpd and surfactant and in water, mix, obtain suspension, described M is a kind of among Ti, Co, Fe, Mg, Al, Cr and the Nb;
In confined conditions, described suspension is heated, obtain the positive electrode presoma;
In inert gas atmosphere, described positive electrode presoma is carried out roasting, obtain anode material for lithium-ion batteries.
6. preparation method according to claim 5 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 lithiums;
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 the manganous hydroxide;
In the oxide that the described M of containing compound is M, hydroxide, nitrate, the acylate one or more;
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 lithiums;
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 the polysaccharide.
7. preparation method according to claim 5, 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 the sulfonic acid.
8. preparation method according to claim 5, it is characterized in that, described P source compound, manganese source compound, the mol ratio that contains phosphorus, manganese, M and lithium in M compound, the Li source compound are (1 ~ 1.1): (0.8 ~ 1): (0.2 ~ 0): (1 ~ 1.1), the described M of containing compound are not 0;
The quality of described carbon-source cpd is P source compound, manganese source compound, contain the 5wt% ~ 15wt% of M compound and Li source compound gross mass;
The quality of described surfactant is P source compound, manganese source compound, contain the 1wt% ~ 10wt% of M compound and Li source compound gross mass.
9. preparation method according to claim 5 is characterized in that, the solid content of described suspension is 10wt% ~ 50wt%.
10. preparation method according to claim 5 is characterized in that, the temperature of described heating is 120 ℃ ~ 280 ℃;
The time of described heating is 3h ~ 20h.
11. preparation method according to claim 5 is characterized in that, the temperature of described roasting is 450 ℃ ~ 750 ℃;
The time of described roasting is 2h ~ 10h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210551815.XA CN102983334B (en) | 2012-12-18 | 2012-12-18 | Anode material for lithium-ion batteries and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210551815.XA CN102983334B (en) | 2012-12-18 | 2012-12-18 | Anode material for lithium-ion batteries and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102983334A true CN102983334A (en) | 2013-03-20 |
| CN102983334B CN102983334B (en) | 2016-03-02 |
Family
ID=47857173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210551815.XA Active CN102983334B (en) | 2012-12-18 | 2012-12-18 | Anode material for lithium-ion batteries and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102983334B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337626A (en) * | 2013-04-27 | 2013-10-02 | 上海交通大学 | LiFexM1-xPO4/mesoporous carbon composite material and preparation method hereof |
| 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 |
| CN103594712A (en) * | 2013-07-18 | 2014-02-19 | 横店集团东磁股份有限公司 | Metal-doped oxidative conductive carbon black cladded lithium manganese phosphate and preparation method thereof |
| 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 |
| CN105110310A (en) * | 2015-08-13 | 2015-12-02 | 天津巴莫科技股份有限公司 | Preparation method for lithium manganese phosphate used for lithium-ion power battery |
| CN108269995A (en) * | 2016-12-30 | 2018-07-10 | 广东天劲新能源科技股份有限公司 | The regulatable ternary precursor of crystal structure, positive electrode and preparation method thereof |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| 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 |
| CN111943285A (en) * | 2020-08-19 | 2020-11-17 | 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 |
| CN114212764A (en) * | 2021-11-30 | 2022-03-22 | 厦门厦钨新能源材料股份有限公司 | Phosphate anode material precursor, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734637A (en) * | 2008-11-20 | 2010-06-16 | 中国科学院理化技术研究所 | Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery |
| CN101320809B (en) * | 2008-07-17 | 2011-02-09 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
| CN102427131A (en) * | 2011-09-09 | 2012-04-25 | 广州市香港科大***研究院 | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery |
-
2012
- 2012-12-18 CN CN201210551815.XA patent/CN102983334B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320809B (en) * | 2008-07-17 | 2011-02-09 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
| CN101734637A (en) * | 2008-11-20 | 2010-06-16 | 中国科学院理化技术研究所 | Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery |
| CN102427131A (en) * | 2011-09-09 | 2012-04-25 | 广州市香港科大***研究院 | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| JIALI LIU ET AL.: "Synthesis of flower-like LiMnPO4/C with precipitated NH4MnPO4•H2O as precursor", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 518, 31 December 2011 (2011-12-31), pages 58 - 62, XP028887378, DOI: 10.1016/j.jallcom.2011.12.134 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103337626A (en) * | 2013-04-27 | 2013-10-02 | 上海交通大学 | LiFexM1-xPO4/mesoporous carbon composite material and preparation method hereof |
| CN103594712A (en) * | 2013-07-18 | 2014-02-19 | 横店集团东磁股份有限公司 | Metal-doped oxidative conductive carbon black cladded lithium manganese phosphate 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 |
| CN105110310A (en) * | 2015-08-13 | 2015-12-02 | 天津巴莫科技股份有限公司 | Preparation method for lithium manganese phosphate used for lithium-ion power battery |
| 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 |
| CN108269995A (en) * | 2016-12-30 | 2018-07-10 | 广东天劲新能源科技股份有限公司 | The regulatable ternary precursor of crystal structure, positive electrode and preparation method thereof |
| CN108400330A (en) * | 2018-03-08 | 2018-08-14 | 蒋央芳 | A kind of preparation method of carbon doping phosphoric acid manganese (III) |
| 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 |
| CN111943285A (en) * | 2020-08-19 | 2020-11-17 | 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 |
| 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 |
| CN114212764A (en) * | 2021-11-30 | 2022-03-22 | 厦门厦钨新能源材料股份有限公司 | Phosphate anode material precursor, preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102983334B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102983334B (en) | Anode material for lithium-ion batteries and preparation method thereof | |
| Liu et al. | On the drastically improved performance of Fe-doped LiMn2O4 nanoparticles prepared by a facile solution-gelation route | |
| Pan et al. | Hydrothermal synthesis of well-dispersed LiMnPO4 plates for lithium ion batteries cathode | |
| Gong et al. | In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries | |
| CN102931405B (en) | Lithium manganese phosphate cathode material and preparation method thereof | |
| CN103022486B (en) | A kind of preparation method of anode material for lithium-ion batteries | |
| US20230322557A1 (en) | Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery | |
| CN102427131A (en) | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery | |
| CN1632970A (en) | Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate | |
| CN101630731A (en) | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof | |
| CN103682266A (en) | Li and Mn codoped manganese phosphate/carbon composite material and preparation method thereof | |
| CN102637873A (en) | Lithium ion battery cathode material and method for preparing same | |
| Xiang et al. | Improved electrochemical performance of Li1. 2Ni0. 2Mn0. 6O2 cathode material for lithium ion batteries synthesized by the polyvinyl alcohol assisted sol-gel method | |
| Fu et al. | Hierarchical porous Li4Mn5O12 nano/micro structure as superior cathode materials for Li-ion batteries | |
| Kong et al. | Fabrication of promising LiFePO4/C composite with a core–shell structure by a moderate in situ carbothermal reduction method | |
| CN103199247A (en) | Preparation method of composite positive material with multi-level conductive network of lithium ion battery | |
| CN104253273A (en) | Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof | |
| CN102623701B (en) | Preparation method for low-temperature nanometer lithium iron phosphate cathode material | |
| CN102623705A (en) | Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof | |
| CN103413944A (en) | Lithium manganese phosphate positive electrode material and preparation method thereof | |
| Zhou et al. | Fabrication of nanoplate Li-rich cathode material via surfactant-assisted hydrothermal method for lithium-ion batteries | |
| Kong et al. | Synthesis of lithium rich layered oxides with controllable structures through a MnO2 template strategy as advanced cathode materials for lithium ion batteries | |
| Qiu et al. | Li1. 2Mn0. 6Ni0. 2O2 with 3D porous rod-like hierarchical micro/nanostructure for high-performance cathode material | |
| CN102110811A (en) | Method for preparing nanoscale lithium ion battery LiFePo4/C anodal material | |
| CN103746117A (en) | Preparation method of magnesium-ion-doped lithium ion battery positive pole lithium vanadium phosphate/carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180312 Address after: West Street in the official Zhejiang city of Ningbo province Zhenhai District 315201 Village No. 1818 Patentee after: NINGBO FULI BATTERY MATERIAL TECHNOLOGY CO., LTD. Address before: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Patentee before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |