CN109904409A - A kind of lithium iron phosphate nano stick/graphene composite material and its preparation method and application - Google Patents
A kind of lithium iron phosphate nano stick/graphene composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of lithium iron phosphate nano stick/graphene composite materials and its preparation method and application; provide firstly a kind of ferrous oxalate/graphene oxide composite material; then the ferrous oxalate/graphene oxide compound is mixed with ammonium dihydrogen phosphate and Lithium acetate dihydrate by certain mol proportion; after mill-drying, carry out pyroreaction under the protection of inert gas to obtain the final product；Lithium iron phosphate nano stick/graphene composite material that the present invention uses two step solid phase method to be prepared, particle is small, particle diameter distribution is uniform, and there is the rodlike structure of 1-dimention nano, the transmission rate of ion can be effectively improved, guarantee that capacity is unattenuated when heavy-current discharge；The addition of graphene further increases material surface electric conductivity, while significantly improving the high rate performance and cycle performance of material；In lithium iron phosphate nano stick/graphene composite material preparation process, reaction condition is easily controllable, easy to operate, low production cost, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields.In particular it relates to a kind of lithium iron phosphate nano stick/stone
Black alkene composite material and preparation method and application.
Background technique
The LiFePO4 of olivine structural is considered as one of most promising power battery anode material, comes with raw material
Many advantages, such as source is abundant, safety and environmental protection, stable cycle performance, but because its structure limit so that electronics and ionic conductivity compared with
It is low, cause its actual capacity lower.Compound its chemical property of improvement that can be apparent of graphene and LiFePO4.
Preparing LiFePO4/graphene oxide composite positive pole method at present is mainly liquid phase method, because of liquid phase method
It can according to need control sample particle diameter size, be uniformly mixed raw material, and then control sample topography.CN2017105575511
Disclose a kind of nano-scale lithium iron phosphate/graphene composite material and its preparation method and application, the LiFePO4/ graphene
The preparation method of nanocomposite is by LiOH/ ethylene glycol solution fast drop to H3PO4In/ethylene glycol solution, then with
FeSO4The mixing of/ethylene glycol solution through solvent thermal reaction and post-processes up to lithium iron phosphate nano piece, and under liquid-phase condition into
Row graphene coated obtains the nanoscale LiFePO for the high current cyclical stability for having excellent4/ graphene composite material.It should
Mole when reaction temperature of raw material in strict control solvent thermal reaction is needed in preparation process, and is needed in reaction process a large amount of
Ethylene glycol not only increase cost of material as solvent while causing a large amount of wastage of material, be not easy to realize industrial production.
The powder granule soilless sticking of conventional solid-state method preparation, fillibility is good, at low cost, yield is big, preparation process is simple, such as
(preparation of Li Qiru graphene-coated lithium iron phosphate positive electrode and its Suzhou chemical property [D] are big by Li Qiru et al.
Learn, 2016.) simple solid phase is used in one text of preparation and its chemical property of graphene-coated lithium iron phosphate positive electrode
Method, using ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate as raw material, organic carbon source glucose and graphene oxide are compounded carbons, at
Function has synthesized LiFePO4/ graphene/C composite, and demonstrate double-contracting and cover LiFePO 4 material than only coated graphite alkene
Sample there is higher specific discharge capacity, but gained LiFePO4/ graphene composite material is graininess, will affect from
The problems such as transmission rate of son, capacity is easy decaying in heavy-current discharge；It is uneven, easy to reunite to exist simultaneously graphene dispersion
The problem of, cause electric conductivity, high rate performance and the cycle performance of composite material may be impacted, while the preparation process has consumption
Energy is big, low efficiency, powder are not thin enough, easy the shortcomings that being mixed into impurity.
It is, thus, sought for a kind of good lithium ion anode material of method processability that method is simple and efficient.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the prior art and deficiencies, provide a kind of ferrous oxalate/oxygen
The preparation method of graphite alkene composite material, the method first by graphene oxide with it is raw materials used it is uniform mix, by right
Ferrous oxalate/graphene oxide composite material of the available club shaped structure of control of reaction condition, and then influence LiFePO4/
Pattern, specific surface area, pore structure and the electric conductivity of graphene presoma, finally obtain the LiFePO4 of the rodlike structure of 1-dimention nano
Nanometer rods/graphene composite material.
The ferrous oxalate being prepared a second object of the present invention is to provide the above method/graphene oxide composite wood
Material.
Third purpose of the present invention is to provide above-mentioned lithium iron phosphate nano stick/graphene composite material.
4th purpose of the invention is to provide the preparation method of above-mentioned lithium iron phosphate nano stick/graphene composite material.
5th purpose of the invention is to provide above-mentioned lithium iron phosphate nano stick/graphene composite material and is preparing lithium-ion electric
Application in pond.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of ferrous oxalate/graphene oxide composite material, this method are as follows: by graphene oxide dispersion and seven
10~14 h of stirring obtain mixed liquor after ferrous sulfate hydrate mixing, state oxalic acid solution stirring 1 is added in mixed liquor then up
~2 h stand 4~10 h in 60~120 DEG C of constant temperature, after filtering, wash, being dry to obtain the final product.
It is first that graphene oxide dispersion and green vitriol and oxalic acid solution is first uniformly mixed in the above method
It closes, solves the problems, such as that graphene dispersion is uneven easy to reunite, it is compound in lithium iron phosphate nano stick/graphene to be conducive to graphene
It is sufficiently mixed in material preparation process；Then, ferrous oxalate/oxidation stone of club shaped structure is obtained by the control to reaction condition
Black alkene composite material, the final pattern for influencing LiFePO4.
Preferably, the constant temperature static conditions are 80~100 DEG C of 6~8 h of standing.
It is highly preferred that the constant temperature static conditions are 90 DEG C of 7 h of standing.
Preferably, the graphene oxide dispersion is by adding graphene oxide into ultrasonic disperse 2 in deionized water
~3 h are obtained.
Preferably, the graphene oxide dispersion, green vitriol, oxalic acid molar ratio be (1~20): (8~
12): (8.5~12.5).
Preferably, the graphene oxide dispersion, green vitriol, oxalic acid molar ratio be (4~15): (8~
12): (8.5~12.5), to obtain the club shaped structure ferrous oxalate/graphene oxide composite material with excellent performance.It is preferred that
Ground, the concentration of the oxalic acid solution mesoxalic acid are 0.4~0.8 mol/L.The present invention is also claimed the above method and is prepared
Ferrous oxalate/graphene oxide composite material.
Meanwhile a kind of lithium iron phosphate nano stick/graphene composite material is also claimed in the present invention, the material is by oxalic acid Asia
Iron/graphene oxide composite material, Lithium acetate dihydrate, ammonium dihydrogen phosphate are prepared through high temperature solid state reaction.
LiFePO4/graphene composite material of the present invention is small with particle and particle diameter distribution is uniform, graphene packet
The advantages of covering uniform and soilless sticking, 1-dimention nano club shaped structure effectively raises the transmission rate of ion, ensure that big electricity
Capacity is unattenuated when banishing electricity；The addition of graphene further improves material surface electric conductivity, makes material high rate performance and follows
Ring performance to being obviously improved.
In addition, a kind of preparation method of lithium iron phosphate nano stick/graphene composite material, the party is also claimed in the present invention
Method are as follows: be in molar ratio by above-mentioned ferrous oxalate/graphene oxide composite material, ammonium dihydrogen phosphate, Lithium acetate dihydrate (8~
12): (8~12): obtaining LiFePO4/graphene composite material presoma after (8.5~12.5) mixing, mill-drying, will be upper
It states presoma and 600~800 DEG C of 6~10 h of heat preservation is warming up to obtain the final product with the heating rate of 2~8 DEG C/min under nitrogen protection.
Specifically, Lithium acetate dihydrate is uniformly mixed first with ferrous oxalate/graphene oxide composite material, is then added
Finely ground ammonium dihydrogen phosphate is ground, and mixture becomes atherosclerotic by powder during the grinding process, continues grinding until becoming powder
End obtains ferric lithium phosphate precursor after dry.Preferably, the heat-retaining condition is 700 DEG C of 8 h of heat preservation.
Preferably, the ferrous oxalate/graphene oxide composite material, ammonium dihydrogen phosphate, Lithium acetate dihydrate be in molar ratio
For 1: 1: 1.05 mixing.
It is further preferred that the drying is 60~100 DEG C of dry 1~3 h.
It is highly preferred that the drying is 80 DEG C of dry 2 h.
The rodlike structure of lithium iron phosphate nano stick/graphene composite material 1-dimention nano being prepared through the invention has
The transmission rate for improving ion of effect, capacity is unattenuated when ensure that heavy-current discharge, has good high rate performance and follows
Ring performance can be used for preparing the positive electrode of battery.
Therefore, the present invention is also claimed above-mentioned lithium iron phosphate nano stick/graphene composite material and is preparing lithium-ion electric
Application in pond.
Inventor has the rodlike knot of 1-dimention nano by creatively working to be prepared using two step solid phase method
LiFePO4/graphene composite material of structure, whole process is easy to operate, low in cost, energy conservation and environmental protection.In addition, graphite oxide
The evenly dispersed electric conductivity and stability for being conducive to improve material of alkene, while improving the high rate performance and cycle performance of material.
Compared with prior art, the invention has the following advantages:
Graphene oxide dispersion, green vitriol, oxalic acid are mixed and are prepared under suitable conditions first by the present invention
Ferrous oxalate/graphene oxide composite material of nano bar-shape structure, solves that graphene dispersion is uneven, and easy to reunite asks
Topic；Then ferrous oxalate/graphene oxide composite material, ammonium dihydrogen phosphate, Lithium acetate dihydrate are mixed through high temperature solid state reaction
A kind of lithium iron phosphate nano stick/graphene composite material of rodlike structure of 1-dimention nano is finally prepared.The present invention uses two
Lithium iron phosphate nano stick/graphene composite material that single-step solid phase reaction method is prepared, particle is small, particle diameter distribution is uniform, graphite
Alkene is evenly coated and soilless sticking, and has the rodlike structure of 1-dimention nano, can effectively improve the transmission rate of ion, guarantees big
Capacity is unattenuated when current discharge；The addition of graphene further increases material surface electric conductivity, while significantly improving material
The high rate performance and cycle performance of material；In lithium iron phosphate nano stick/graphene composite material preparation process, reaction condition is easy to
Control, easy to operate, low production cost, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is ferrous oxalate/graphene oxide SEM figure that embodiment 1 is prepared；
Fig. 2 is lithium iron phosphate nano stick/graphene SEM figure that embodiment 1 obtains；
Fig. 3 is the SEM figure for the LiFePO4 that comparative example 1 obtains；
Fig. 4 is respectively lithium iron phosphate nano stick/graphene and LiFePO4 X-ray that embodiment 1 and comparative example 1 are prepared
Powder diagram；
Fig. 5 is respectively lithium iron phosphate nano stick/graphene and LiFePO4 0.2C that embodiment 1 and comparative example 1 are prepared
First charge-discharge curve；
Fig. 6 is respectively lithium iron phosphate nano stick/graphene and LiFePO4 multiplying power that embodiment 1 and comparative example 1 are prepared
Performance curve；
Fig. 7 is respectively lithium iron phosphate nano stick/graphene and LiFePO4 constant current that embodiment 1 and comparative example 1 are prepared
Charge and discharge cycles curve.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
The preparation of 1 lithium iron phosphate nano stick of embodiment/graphene composite material
One, method
1, ferrous oxalate/graphene oxide composite material preparation
4 mmoL graphene oxides are dissolved in deionized water first, 2 h of ultrasonic disperse obtains graphene oxide dispersion, so
10 mmoL green vitriols are added in backward above-mentioned graphene oxide dispersion, stir 12 h, obtain mixed liquor, then to
It is poured slowly into the oxalic acid solution of 10.5 mmoL in mixed liquor, persistently stirs after 1.5 h that 90 DEG C of 7 h of heating make it in drying box
Reaction completely, obtains solid sediment；Three times by above-mentioned solid sediment filtering and washing, levigate sub- up to oxalic acid after vacuum drying
Iron/graphene oxide composite material.
2, lithium iron phosphate nano stick/graphene composite material preparation
By the above-mentioned ferrous oxalate/graphene oxide of 10 mmoL and 10.5 mmoL Lithium acetate dihydrate ground and mixed, 15 min to mixing
Sufficiently, 10 mmoL ammonium dihydrogen phosphates are then added and grind 30 min, mixture becomes atherosclerotic by powder during the grinding process,
Continue grinding until becoming powder, powder obtained into LiFePO4/graphene composite material presoma after 80 DEG C of dry 2 h,
Then LiFePO4/graphene composite material presoma is placed under nitrogen protection, with the heating rate of 6 DEG C/min at 700 DEG C
8 h are kept the temperature, cooled to room temperature is up to lithium iron phosphate nano stick/graphene composite material.
Two, result
Ferrous oxalate/graphene oxide the shape characteristic being prepared by embodiment 1 is as shown in Figure 1, as can be seen from the figure
Gained ferrous oxalate nanometer rods are uniformly dispersed, and size is uneven, and for diameter at 0.5~1.2 μm, nanorod surfaces are more smooth, silk
The graphene oxide of shape is uniformly coated on its surface, by the way that graphene oxide and the compound of raw material can be reduced oxidation stone
The accumulation of black alkene lamella, so that it is mixed more evenly with raw material.Gained lithium iron phosphate nano stick/graphene composite material shape
Looks feature is as shown in Fig. 2, graphene is made of many very thin nanometer sheets as seen from the figure, due to the effect of stress, nanometer sheet
Edge curl.LiFePO4 is made of nanometer rods, and size is uneven, and diameter remains ferrous oxalate at 0.6~1.0 μm
Rod-like shape, be coated on phosphoric acid iron surface to the graphene uniform of fold, can effectively reduce in this way its crystallite dimension and
Prevent the reunion of nano particle.
The preparation of 2 lithium iron phosphate nano stick of embodiment/graphene composite material
One, method
10 mmoL graphene oxides: being dissolved in deionized water by the preparation of ferrous oxalate/graphene oxide composite material first,
2 h of ultrasonic disperse, obtains graphene oxide dispersion, states 8 mmoL seven hydration is added in graphene oxide dispersion then up
Ferrous sulfate stirs 10 h, obtains mixed liquor, then be poured slowly into the oxalic acid solution of 8.5 mmoL into mixed liquor, persistently stir 2
80 DEG C of 8 h of heating react it completely in drying box after h, obtain solid sediment；By above-mentioned solid sediment filtering and washing
Three times, levigate up to ferrous oxalate/graphene oxide composite material after vacuum drying.
The preparation of lithium iron phosphate nano stick/graphene composite material: by the above-mentioned ferrous oxalate/graphene oxide of 8 mmoL with
8.5 mmoL Lithium acetate dihydrate ground and mixeds are abundant, then add 8 mmoL ammonium dihydrogen phosphates and grind 30 min, ground
Mixture becomes atherosclerotic by powder in journey, continues grinding until becoming powder, powder is obtained phosphoric acid after dry 3 h at 60 DEG C
Then LiFePO4/graphene composite material presoma is placed under nitrogen protection by iron lithium/graphene composite material presoma,
With the heating rate of 2 DEG C/min in 600 DEG C of 10 h of heat preservation, cooled to room temperature is multiple up to lithium iron phosphate nano stick/graphene
Condensation material.
The preparation of 3 lithium iron phosphate nano stick of embodiment/graphene composite material
One, method
15 mmoL graphene oxides: being dissolved in deionized water by the preparation of ferrous oxalate/graphene oxide composite material first,
2 h of ultrasonic disperse, obtains graphene oxide dispersion, states 12 mmoL, seven water is added in graphene oxide dispersion then up
Ferrous sulfate is closed, 14 h is stirred, obtains mixed liquor, then be poured slowly into the oxalic acid solution of 12.5 mmoL into mixed liquor, persistently stir
It mixes after 1 h that 100 DEG C of 6 h of heating react it completely in drying box, obtains solid sediment；Above-mentioned solid sediment is filtered
Washing is three times, levigate up to ferrous oxalate/graphene oxide composite material after vacuum drying.
Lithium iron phosphate nano stick/graphene composite material preparation: by the above-mentioned ferrous oxalate/graphene oxide of 12 mmoL
It is abundant with 12.5 mmoL Lithium acetate dihydrate ground and mixeds, it then adds 12 mmoL ammonium dihydrogen phosphates and grinds 30 min, grinding
Mixture becomes atherosclerotic by powder during mill, continues grinding until becoming powder, powder is obtained after 100 DEG C of dry 1 h
Then LiFePO4/graphene composite material presoma is placed in nitrogen protection by LiFePO4/graphene composite material presoma
Under, with the heating rate of 8 DEG C/min in 800 DEG C of 6 h of heat preservation, cooled to room temperature is up to lithium iron phosphate nano stick/graphene
Composite material.
Comparative example 1
One, method
The commercially available ferrous oxalate of 4 mmoL, 10.5 mmoL Lithium acetate dihydrates, the mixing of 10 mmoL ammonium dihydrogen phosphates are fully ground mixed
Conjunction is placed in 80 DEG C of conditions dry 2 h and obtains LiFePO 4 material presoma, is then placed in LiFePO 4 material presoma
Under nitrogen protection, with the heating rate of 8 DEG C/min in 700 DEG C of 8 h of heat preservation, cooled to room temperature is up to LiFePO 4 material.
Lithium iron phosphate nano stick/graphite that the LiFePO 4 material being prepared according to the above method and embodiment 1 are obtained
Alkene composite material carries out X-ray detection, the detection of 0.2 C first charge-discharge, high rate performance detection, constant current charge-discharge cyclicity respectively
It can detection.
Two, result
The result of this comparative example as shown in figure 3 to figure 7, as seen in Figure 3, the LiFePO4 pattern that comparative example 1 is prepared
For the spheric granules that surface is smooth, diameter has certain reunion in 150 nm or so, between particle.This comparative example 1 and embodiment 1 are obtained
To lithium iron phosphate nano stick/graphene oxide compare, illustrate to be prepared by two steps solid phase method described in embodiment 1
Lithium iron phosphate nano stick/graphene good forming effect.
From fig. 4, it can be seen that the LiFePO4 crystal structure all having the same that embodiment 1 and comparative example 1 are prepared,
Single rhombic system olivine structural is belonged to, does not occur stone in lithium iron phosphate nano stick/grapheme material XRD spectrum
The characteristic peak of black alkene illustrates that a small amount of graphene addition will not change the crystal structure of LiFePO4.
From Fig. 5~7 as can be seen that the LiFePO4 first discharge specific capacity that comparative example 1 synthesizes is 156 mAh/g, implement
Lithium iron phosphate nano stick/graphene composite material first discharge specific capacity that example 1 obtains is 154 mAh/g；By 0.2 C →
The latter two can be restored to the initial specific capacity of 0.2 C to the C of C → 0.5 of C → 10 of C → 5 of 0.5 C → 1C → 2 charge and discharge cycles, from
0.2 C is followed successively by 156 mAh/g, 133 mAh/g, 122 mAh/g, 120 mAh/ to 10 C LiFePO 4 material specific discharge capacities
G, 111 mAh/g and 97 mAh/g, lithium iron phosphate nano stick/graphene composite material specific discharge capacity be followed successively by 154 mAh/g,
142 mAh/g, 133 mAh/g, 131 mAh/g, 117 mAh/g and 111 mAh/g, specific capacity is compared with phosphorus when 2 C, 5 C and 10 C
Sour iron lithium material improves 7.3%, 5.4% and 14.4%；LiFePO 4 material still has initial hold after 50 charge and discharge cycles
The 98.9% of amount, lithium iron phosphate nano stick/grapheme material specific capacity into after crossing 100 charge and discharge cycles still have initial capacity
100%.Illustrate that the lithium iron phosphate nano being prepared by two step solid phase method stick/graphene oxide composite material is advantageous
In the electric conductivity and stability that improve material, and then improve the high rate performance and cycle performance of material.
Comparative example 2
By 4 mmoL graphene oxides, 10 mmoL green vitriols, the oxalic acid solution of 10.5 mmoL, 10.5 mmoL bis-
Water acetic acid lithium, the mixing of 10 mmoL ammonium dihydrogen phosphates are fully ground mixing and are placed on 80 DEG C of 2 h of drying and obtain LiFePO4/graphite
Then LiFePO4/graphene composite material presoma is placed under nitrogen protection, with 6 DEG C/min by alkene composite material precursor
Heating rate in 700 DEG C of 8 h of heat preservation, cooled to room temperature is up to lithium iron phosphate nano stick/graphene composite material.
By lithium iron phosphate nano stick/graphene composite material that this comparative example 2 obtains and the LiFePO4 that embodiment 1 obtains
Nanometer rods/graphene composite material compares.
Two, result
The graininess LiFePO4 nanometer rods/graphene composite material rough surface obtained by this comparative example 2, size distribution compared with
Width, about 600 nm of the particle of larger size, graphene contact loosely with the irregular LiFePO4 of pattern, and nano particle is rolled into a ball
Poly- phenomenon；In addition, compared with Example 1, lithium iron phosphate nano stick/graphene composite material ion that this comparative example 2 obtains
Transmission rate is not high, and chemical property is bad, and capacity attenuation is serious when heavy-current discharge.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of ferrous oxalate/graphene oxide composite material, which is characterized in that by graphene oxide dispersion
10~14 h are stirred after mixing with green vitriol and obtain mixed liquor, are stated addition oxalic acid solution in mixed liquor then up and are stirred
It mixes 1~2 h and stands 4~10 h in 60~120 DEG C of constant temperature, after filtering, wash, being dry to obtain the final product.
2. method according to claim 1, which is characterized in that the constant temperature static conditions are 80~100 DEG C of 6~8 h of standing.
3. method according to claim 1, which is characterized in that the graphene oxide dispersion, green vitriol, grass
The molar ratio of acid is (1~20): (8~12): (8.5~12.5).
4. method according to claim 3, which is characterized in that the graphene oxide dispersion, green vitriol, grass
The molar ratio of acid is (4~15): (8~12): (8.5~12.5).
5. method according to claim 1, which is characterized in that the concentration of the oxalic acid solution mesoxalic acid is 0.4~0.8
mol/L。
6. ferrous oxalate/the graphene oxide composite material being prepared by any the method for Claims 1 to 5.
7. a kind of lithium iron phosphate nano stick/graphene composite material, which is characterized in that compound by ferrous oxalate/graphene oxide
Material, Lithium acetate dihydrate, ammonium dihydrogen phosphate are prepared through high temperature solid state reaction.
8. a kind of preparation method of lithium iron phosphate nano stick/graphene composite material, which is characterized in that will be described in claim 5
Ferrous oxalate/graphene oxide composite material, ammonium dihydrogen phosphate, Lithium acetate dihydrate are (8~12) in molar ratio: (8~12):
(8.5~12.5) LiFePO4/graphene composite material presoma is obtained after mixing, mill-drying, by above-mentioned presoma in nitrogen
600~800 DEG C of 6~10 h of heat preservation are warming up to obtain the final product with the heating rate of 2~8 DEG C/min under gas shielded.
9. method according to claim 8, which is characterized in that the ferrous oxalate/graphene oxide composite material, di(2-ethylhexyl)phosphate
The molar ratio of hydrogen ammonium and Lithium acetate dihydrate is 1: 1: 1.05.
10. the stick of lithium iron phosphate nano described in claim 7/graphene composite material is preparing the application in lithium ion battery.
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| CN112151780A (en) * | 2020-09-21 | 2020-12-29 | 江苏塔菲尔新能源科技股份有限公司 | Nano lithium iron phosphate/graphene oxide composite material and preparation method and application thereof |
| CN113594434A (en) * | 2021-07-21 | 2021-11-02 | 昆明理工大学 | Preparation method of dandelion-shaped core-shell structure silicon-ferrous oxalate lithium ion battery material |
| CN114195115A (en) * | 2021-11-17 | 2022-03-18 | 合肥国轩高科动力能源有限公司 | Modification method of lithium iron phosphate composite material |
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| CN114195115B (en) * | 2021-11-17 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Modification method of lithium iron phosphate composite material |
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