CN102347477A - Method for preparing high-performance lithium iron phosphate / carbon anode material by microwave method - Google Patents
Method for preparing high-performance lithium iron phosphate / carbon anode material by microwave method Download PDFInfo
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- CN102347477A CN102347477A CN201010245258XA CN201010245258A CN102347477A CN 102347477 A CN102347477 A CN 102347477A CN 201010245258X A CN201010245258X A CN 201010245258XA CN 201010245258 A CN201010245258 A CN 201010245258A CN 102347477 A CN102347477 A CN 102347477A
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Abstract
The invention discloses a method for preparing a lithium iron phosphate / carbon anode material under a microwave heating condition with vacuum-protected environment; microwave heating is adopted to promote the graphitization of the carbon material, and the growth of lithium iron phosphate particles is inhibited in vacuum-protected environment; and thus a nanometer lithium iron phosphate / carbon anode material with high conductivity is obtained. The lithium iron phosphate / carbon material prepared by the invention has a conductivity of more than 10-4 S/cm, a particle size of less than 200 nanometers, a specific capacity of more than 140 mAh/g, and has comprehensive performance indexes higher than those of materials prepared by resistor heating in inert atmosphere protected environment under a same condition; and the preparation method is simple in operation, and is applicable to large-scale production.
Description
Technical field
The invention belongs to the energy storage material technical field; Be specifically related under vacuum atmosphere and the microwave selective heating condition; Reach and both control the LiFePO4 particle to nano-scale; Improve the degree of graphitization of material with carbon element again; Thereby improve the electronics and the lithium ion conductive of LiFePO4/carbon composite anode material, improve the high rate performance of material.
Background technology
Exhausted day by day along with traditional fossil energy, and to the pay attention to day by day of environmental protection problem, people are urgent for the increasing demand of novel green high efficient energy sources.Lithium ion battery has received attention especially as the new forms of energy with powerful competitive advantage, and except the extensive use in existing small portable battery, the development prospect of lithium ion battery in high-power, high-octane electrokinetic cell allows the people expect especially.Electrode material is the key factor that influences the lithium ion battery performance.Discover; LiFePO 4 material has outstanding advantage because of its high-energy-density and high safety performance in power lithium-ion battery; But its low conductivity has limited the direct application of this material again, need come the improvement of performance in addition through means such as modification and doping.Means such as traditional material with carbon element coating, conducting polymer doping and metal nanoparticle mixing all can improve the conductivity of iron phosphate lithium positive pole; But improve constantly along with what battery performance was required; Especially power lithium-ion battery is to the dual high request of energy density and power density, and the LiFePO4 method of modifying of development of new becomes urgent day by day with the further lifting that obtains battery performance.
Though LiFePO
4Have plurality of advantages, but also there is self intrinsic shortcoming in it, relatively poor (conductance is 10 like conductivity
-9-10
-10S/cm), the lithium ion diffusion velocity slow (10
-14Cm
2/ s), low, the poor processability of tap density etc., seriously restricted LiFePO
4The practicalization of material.
In order to improve the electric conductivity of material; Usually improve a grain conduction at LiFePO4 particle surface coated with conductive material; Internal electrical conductance at lattice position impurity ion raising material improves ionic conductivity through nanometer minimizing ions diffusion path simultaneously.Above method all can effectively improve the LiFePO 4 material conductivity, improves high rate capability.With regard to particle surface coats; The selection of surface coating is more; Comprise conducting metal, oxide, metal nitride etc. and compound thereof, wherein carbon and carbon-based material be because it is cheap, and preparation is simple and to help advantage status in practicalization such as nanometerization particularly outstanding.Usually carbonaceous organic material and various forms of carbon etc. can be dispersed in the presoma/LiFePO4 product of LiFePO4, carry out carbonization, thereby obtain the LiFePO4/carbon composite anode material of high conductivity through Overheating Treatment.Yet in heat treatment process, SP can appear in carbonaceous material
3, Sp
2Reach hydridization forms such as SP, wherein Sp
3The conductivity of hybrid material (like diamond) is very low, belongs to insulator; Sp
2Hybrid material (like graphite) conductivity is high, is good conductor; The SP hybrid material is comparatively complicated, and its electric conductivity is also relatively poor.
In the research of graphite material; The graphitization that can know material with carbon element needs higher temperature (much larger than 800 degree) usually; Yet under so high temperature; LiFePO 4 material can grow into micron order; Also having dephasign simultaneously exists; Have a strong impact on the lithium ion conductivity of LiFePO 4 material, thereby reduce its high magnification chemical property.And under lower growth temperature, although the particle size of LiFePO4 is easy to control, the graphitization of material with carbon element is lower, so conductivity is lower.
Microwave heating method has strong selectivity, and high conductivity material and easy polarization material have strong absorption microwave ability usually.For example the wave-sucking performance of material with carbon element is stronger, and the wave-sucking performance of LiFePO4 relatively a little less than.When therefore adopting microwave heating, can make the intensification of material with carbon element very fast, and the temperature of LiFePO 4 material is slower, thereby produces high temperature, material with carbon element generation graphitization is transformed in the part.
When conventional method prepares LiFePO 4 material; All under inert atmosphere, carry out; And vacuum atmosphere can make LiFePO 4 material when sloughing surface chemistry water; Stop the reunion of particle; And then the growth of inhibition LiFePO4 particle; Therefore adopt vacuum atmosphere protection heating, can bear higher heating-up temperature and be unlikely to make particle to be grown up rapidly.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of microwave method prepares LiFePO4/carbon composite anode material; Use microwave and vacuum heat mode simultaneously; Utilize microwave heating to produce localized hyperthermia, promote the graphitization of material with carbon element, improve the intergranular conductivity of LiFePO4.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:, a kind of microwave method prepares the method for LiFePO4/carbon composite anode material; It is characterized in that step is: the presoma of lithium source, source of iron, phosphorus source and carbon source is taken by weighing to be placed in the solvent by a certain percentage evenly mix; Dry back is under vacuum protection atmosphere; Heat-treat as heating source with microwave; Said heat treatment is divided into two sections; Wherein first section temperature is 200～500 ℃, and sintering time is 0.5～5 hour; Second section annealing temperature is 200～900 ℃, and sintering time is 1～10 hour; Promptly obtain LiFePO4/carbon composite anode material after the cooling.
As improvement, said microwave heating temperature is a room temperature to 900 ℃, and be 1.5～15 hours heating time; The vacuum degree of said vacuum protection atmosphere is 0～10
4Handkerchief adopts common vacuum plant or high-vacuum installation to carry out.
Preferably, said microwave heating temperature is 600～800 ℃, and said vacuum degree is 10
2～10
-1Handkerchief.
The lithium in said lithium source, source of iron, phosphorus source, iron, phosphorus mol ratio are 0.8～1.2: 0.8～1.2: 0.8～1.2; Described lithium source presoma is one or more the combination in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium bromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or the lithium phosphate; Described source of iron presoma is one or more the combination in iron, ferrous oxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous nitrate, ferrous phosphate, ferrous oxalate, ferrous acetate or the ferrous citrate; Described phosphorus source presoma is one or more the combination in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums or the phosphorus pentoxide.
Preferably, the mol ratio of said lithium, iron, phosphorus is 0.95～1.05: 1: 1.
Said carbon source is the luxuriant and rich with fragrance terpolymer of benzene naphthalene, benzene naphthalene luxuriant and rich with fragrance bipolymer, benzene anthracene bipolymer, gather one or more of benzene, soluble starch, polyvinyl alcohol, sucrose, glucose, urea, phenolic resins, furfural resin, Delanium, natural stone mill, superconduction acetylene black, acetylene black, carbon black or mesocarbon bead, and carbon content accounts for 1%～10% of LiFePO4 quality in the end-product.
Described solvent is inorganic or organic reagent or mixed liquor, comprises one or more of water, alcohols, ketone, ethers, acids, Polymer Solution, and the quality of solvent is 0.3～10 times of other reactant presoma quality sums.
Improve, described mixing is carried out through the mode of mechanical agitation or high energy milling again, and incorporation time is 1～24 hour.
At last, the said dry means of spray drying, direct drying or vacuum filtration that adopt are carried out.
Compared with prior art, the invention has the advantages that:
Adopt the heat treatment mode of microwave and vacuum protection atmosphere, adopt microwave heating, owing to the wave-sucking performance of material with carbon element is stronger, and the wave-sucking performance of LiFePO4 relatively a little less than.Therefore during microwave heating, can make the intensification of material with carbon element very fast, and the intensification of LiFePO 4 material is slower, thereby produces high temperature, material with carbon element generation graphitization is transformed in the part.And vacuum atmosphere can make LiFePO 4 material when sloughing surface chemistry water, stop the reunion of particle; And then the growth of inhibition LiFePO4 particle; Finally can be under higher preparation temperature; Realize high graphitization and nanometerization simultaneously; Reach all higher effect of ionic conductivity and electronic conductivity, improve the chemical property of composite positive pole.
The invention solves when having temperature drift in the conventional heat treated, although the material with carbon element degree of graphitization is high, the LiFePO4 particle is easy to grow up and makes the shortcoming that lithium ion conductivity is lower; And heat treatment temperature is when on the low side, and the LiFePO4 particle is less, but the lower defective of material with carbon element degree of graphitization.LiFePO4/carbon composite anode material that the present invention makes, its conductivity can surpass 10
-4S/cm, specific capacity is greater than 140mAh/g, and less than 500 nanometers, the lithium ion diffusion coefficient reaches 10 to LiFePO4 primary granule controllable size built in D50
-11Cm
2/ s.Method used in the present invention is simple, easy to operate, practical, and effect is remarkable, is suitable for the industrialization running.
Description of drawings
Fig. 1 is N
2Resistance-type heats the SEM figure of the LiFePO4/material with carbon element of 800 ℃ of (b) heat treatments preparations of microwave heating under 800 ℃ (a) and the vacuum protection under the protection;
Fig. 2 is that the chemical property of corresponding sample among Fig. 1 compares;
Fig. 3 is in the instance 1, and the heat of water in the precursor samples of not heat-treating (m=18) is analyzed a mass spectrogram;
Wherein 100～200 ℃ (among the figure 1) locates corresponding the decomposition of physical absorption water; 200～300 ℃ (among figure 2) corresponding the decomposition and the crystallization water in the reactant presoma of glucose decompose, 300～400 ℃ (among figure 3) corresponding the chemisorbed water decomposition of particle surface.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Choose lithium source, source of iron, phosphorus source and carbon source precursor body; Take by weighing by a certain percentage and be placed in the solvent; After in high energy ball mill, mixing; Dry; And place vacuum atmosphere oven in 350 ℃ of heat treatment 2h, and then between 500 ℃～900 ℃, annealed 2～10 hours, be cooled to room temperature; Obtain required LiFePO4/material with carbon element, microwave heating is used in heat treatment wherein.
The atmosphere protection that uses is vacuum protection, can use common vacuum plant or high-vacuum installation, and vacuum degree is 0～10
4Handkerchief, preferred vacuum degree is 10
2～10
-1Handkerchief.
In the heat treatment process, use microwave as heating source, microwave applicator can be selected common equipment on the market for use, and heating-up temperature is 200 to 900 ℃, and preferred temperature is 600～800 ℃, and be 0.5～10 hour heating time.
Presoma among the present invention comprises at least and contains lithium, iron content and phosphorous compound, its lithium: iron: the mol ratio of phosphorus is 0.8～1.2: 0.8～1.2: 0.8～1.2, and lithium in the preferred version: iron: the mol ratio of phosphorus is 0.95～1.05: 1: 1; The described lithium presoma that contains is one or more the combination in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium bromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate, the lithium phosphate; Described iron content presoma is one or more the combination in iron, ferrous oxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous nitrate, ferrous phosphate, ferrous oxalate, ferrous acetate, the ferrous citrate; Described phosphorous presoma is the combination that a kind of or youngster in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums, the phosphorus pentoxide plants.
Employed carbon source can be selected from and well known to a person skilled in the art the luxuriant and rich with fragrance terpolymer of benzene naphthalene, benzene naphthalene luxuriant and rich with fragrance bipolymer, benzene anthracene bipolymer, gather one or more of benzene, soluble starch, polyvinyl alcohol, sucrose, glucose, urea, phenolic resins, furfural resin, Delanium, natural stone mill, superconduction acetylene black, acetylene black, carbon black and mesocarbon bead among the present invention; Wherein in the end-product; Residual carbon content accounts for 0.1%～20% of LiFePO4 quality; Generally 0.1%～10%, preferred content is 2%～5%.
Method used in the present invention comprises, the solvent of indication comprises inorganic and organic reagent or mixed liquor, and like water, alcohols, ketone, ethers, acids, Polymer Solution etc. one or more, solvent quality is 0.3～10 times of other reactant presoma sums.
Described mixing is carried out through the mode of mechanical agitation or high energy milling.
Described drying can adopt means such as spray drying, direct drying or vacuum filtration to carry out.
Further specify with instantiation below
Embodiment 1 (contrast test)
Choose ferrous oxalate, lithium hydroxide and ammonium dihydrogen phosphate raw material; 1: 1.02: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; 8% glucose that adds the above-mentioned raw materials quality; Make solid content reach 50% simultaneously, in high energy ball mill, mix 7 hours after evenly, spray drying; Place the resistance-type heating furnace then; Under argon shield,, behind 800 ℃ of heat treatment 10h, be cooled to room temperature then, obtain required LiFePO4/carbon composite anode material at 350 ℃ of heat treatment 2h.
The stereoscan photograph of gained material is seen Fig. 1 a, can see that wherein particle can grow to several microns.
Electro-chemical test shows that (Fig. 2 a), the capacity of this material is 101mAh/g.
This conductivity of electrolyte materials is 2X10
-5S/cm.
Choose ferrous oxalate, lithium hydroxide and ammonium dihydrogen phosphate raw material; 1: 1.02: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; 8% glucose that adds the above-mentioned raw materials quality; Make solid content reach 50% simultaneously, in high energy ball mill, mix 7 hours after evenly, spray drying; Place microwave oven then; Down at 350 ℃ of heat treatment 2h, behind 800 ℃ of heat treatment 10h, be cooled to room temperature in the vacuum atmosphere protection then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 5X10
1Handkerchief.
The stereoscan photograph of gained material is seen Fig. 1 b, can see that wherein particle is about the 100-300 nanometer.
Electro-chemical test shows (Fig. 2 b), and the capacity of this material is 154mAh/g.
This conductivity of electrolyte materials is 5X10
-3S/cm.
Choose ferrous citrate, lithium hydroxide and ammonium dihydrogen phosphate raw material; 1: 1.02: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; 8% polyvinyl alcohol that adds the above-mentioned raw materials quality; Wherein solid content reaches 50%, after in high energy ball mill, mixing, sparge dry after; Place microwave oven then; Down at 350 ℃ of heat treatment 2h, behind 650 ℃ of heat treatment 10h, be cooled to room temperature in the vacuum atmosphere protection then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 10
2Handkerchief.
The capacity of this material is 158mAh/g, and conductivity is about 5X10
-5S/cm.
Embodiment 4
Choose ferrous oxalate, lithium carbonate and ammonium dihydrogen phosphate raw material; 1: 0.5: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; 8% phenolic resins that adds the above-mentioned raw materials quality; Wherein solid content reaches 50%, after in high energy ball mill, mixing, after the spray drying; Place microwave oven then; Down at 350 ℃ of heat treatment 2h, behind 700 ℃ of heat treatment 10h, be cooled to room temperature in the vacuum atmosphere protection then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 10
2Handkerchief.
The capacity of this material is 153mAh/g, and conductivity is about 5.3X10
-3S/cm.
Embodiment 5
Choose ferrous oxalate, lithium hydroxide and phosphate raw material; 1: 1.02: 1 in molar ratio ratio takes by weighing and is placed in the ethanolic solution; 8% phenolic resins that adds the above-mentioned raw materials quality; Wherein solid content reaches 50%; After in high energy ball mill, mixing, after the spray drying, protect down at 350 ℃ of heat treatment 2h in vacuum atmosphere; Behind 700 ℃ of heat treatment 10h, be cooled to room temperature then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 10
2Handkerchief.
The capacity of this material is 159mAh/g, and conductivity is about 3.8X10
-5S/cm.
Embodiment 6
Choose ferrous oxalate, lithium hydroxide and ammonium dihydrogen phosphate raw material; 1: 1.02: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; Adding 8% of above-mentioned raw materials quality gathers benzene; Wherein solid content reaches 50%; After in high energy ball mill, mixing; Down at 350 ℃ of heat treatment 2h, behind 850 ℃ of heat treatment 10h, be cooled to room temperature in the vacuum atmosphere protection then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 10 ° of handkerchiefs.
The capacity of this material is 150mAh/g, and conductivity is about 4.3X10
-3S/cm.
Embodiment 7
Choose ferrous oxalate, lithium hydroxide and ammonium dihydrogen phosphate raw material; 1: 0.98: 1 in molar ratio ratio takes by weighing and is placed in the aqueous solution; 8% phenolic resins that adds the above-mentioned raw materials quality; Wherein solid content reaches 50%; After in high energy ball mill, mixing, after the spray drying, protect down at 350 ℃ of heat treatment 2h in vacuum atmosphere; Behind 700 ℃ of heat treatment 10h, be cooled to room temperature then, obtain required LiFePO4/carbon composite anode material.Wherein vacuum degree is 10
3Handkerchief
The capacity of this material is 146mAh/g, and conductivity is about 2.5X10
-5S/cm.
Following instance is to carry out electrochemical property test with the conductivity test of above-mentioned LiFePO4/material with carbon element with after being assembled into battery
Embodiment 8
LiFePO4/material with carbon element is pressed into cylindric lamella, and wherein the lamella diameter is the D=13 millimeter, and thickness is the L=2 millimeter, and institute's working pressure is 20Mp.
Lamella is plated conductive silver paste, make the resistance of same lamella less than 10
-2Ohm uses two electrode method test pole sheet resistor ρ, obtains conductivity=L/D ρ.
Embodiment 9
With positive electrode active materials, PVDF, conductive acetylene black be to join in N-methyl pyrrolidone at 80: 5: 15 by mass ratio; After magnetic agitation is even; Positive plate is processed in oven dry; And with glove box in be assembled into 2032 button cells; Wherein negative pole is the lithium sheet; Barrier film is a polypropylene, and electrolyte is 1M LiPF6, and electrolyte quality is than being EC: DMC: EMC=1: 1: 1.
Probe temperature is 25 ℃ of room temperatures, and voltage range is 2.0-4.2V, and current density is 0.1C=17mAh/g.
Above embodiment illustrates that the heat treatment mode that adopts microwave and vacuum protection atmosphere can promote the graphitization of material with carbon element, suppresses the growth of LiFePO4 particle, increases the intergranular conductivity of LiFePO4, improves the conductance and the capacity of LiFePO4/material with carbon element.
Claims (9)
1. a microwave method prepares the method for LiFePO4/carbon composite anode material; It is characterized in that step is: the presoma of lithium source, source of iron, phosphorus source and carbon source is taken by weighing to be placed in the solvent by a certain percentage evenly mix; Dry back is under vacuum protection atmosphere; Heat-treat as heating source with microwave; Said heat treatment is divided into two sections; Wherein first section temperature is 200～500 ℃, and sintering time is 0.5～5 hour; Second section annealing temperature is 200～900 ℃, and sintering time is 1～10 hour; Promptly obtain LiFePO4/carbon composite anode material after the cooling.
2. method according to claim 1 is characterized in that said microwave heating temperature is 200 to 900 ℃, and be 1.5～15 hours heating time; The vacuum degree of said vacuum protection atmosphere is 0～104 handkerchief, adopts common vacuum plant or high-vacuum installation to carry out.
3. method according to claim 2 is characterized in that said microwave heating temperature is 600～800 ℃, and said vacuum degree is 102～10-1 handkerchief.
4. method according to claim 1 is characterized in that lithium, iron, the phosphorus mol ratio in said lithium source, source of iron, phosphorus source is 0.8～1.2: 0.8～1.2: 0.8～1.2; Described lithium source presoma is one or more the combination in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium bromide, lithium fluoride, lithium nitride, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or the lithium phosphate; Described source of iron presoma is one or more the combination in iron, ferrous oxide, di-iron trioxide, ferrous sulfate, ferric phosphate, ferrous nitrate, ferrous phosphate, ferrous oxalate, ferrous acetate or the ferrous citrate; Described phosphorus source presoma is one or more the combination in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, ferrous ammonium phosphate, phosphoric acid hydrogen two lithiums or the phosphorus pentoxide.
5. method according to claim 4, the mol ratio that it is characterized in that said lithium, iron, phosphorus is 0.95～1.05: 1: 1.
6. method according to claim 1; It is characterized in that said carbon source is the luxuriant and rich with fragrance terpolymer of benzene naphthalene, benzene naphthalene luxuriant and rich with fragrance bipolymer, benzene anthracene bipolymer, gathers one or more of benzene, soluble starch, polyvinyl alcohol, sucrose, glucose, urea, phenolic resins, furfural resin, Delanium, natural stone mill, superconduction acetylene black, acetylene black, carbon black or mesocarbon bead that carbon content accounts for 1%～10% of LiFePO4 quality in end-product.
7. method according to claim 1; It is characterized in that described solvent is inorganic or organic reagent or mixed liquor; Comprise one or more of water, alcohols, ketone, ethers, acids, Polymer Solution, the quality of solvent is 0.3～10 times of other reactant presoma quality sums.
8. method according to claim 1 is characterized in that described mixing carries out through the mode of mechanical agitation or high energy milling, and incorporation time is 1～24 hour.
9. method according to claim 1 is characterized in that the means of said dry employing spray drying, direct drying or vacuum filtration are carried out.
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| CN114094058A (en) * | 2021-11-16 | 2022-02-25 | 杭州电子科技大学 | Preparation method of lithium phosphide electrode based on microwave method |
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| CN111268741A (en) * | 2020-02-11 | 2020-06-12 | 山东大学 | Method and device for batch and controllable preparation of graphite carbon-coated metal/metal oxide nanoparticles and application of graphite carbon-coated metal/metal oxide nanoparticles |
| CN112875766A (en) * | 2021-01-28 | 2021-06-01 | 山东宏匀纳米科技有限公司 | Method for preparing ternary cathode material by microwave heating solution method with carbon source added |
| CN114094058A (en) * | 2021-11-16 | 2022-02-25 | 杭州电子科技大学 | Preparation method of lithium phosphide electrode based on microwave method |
| CN114094058B (en) * | 2021-11-16 | 2023-12-29 | 杭州电子科技大学 | Preparation method of lithium phosphide electrode based on microwave method |
| CN115000347A (en) * | 2022-05-26 | 2022-09-02 | 广东奥德迈新能源有限责任公司 | Modified lithium iron oxide positive pole piece, battery comprising same and preparation method |
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