CN103367728A - Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method - Google Patents

Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method Download PDF

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CN103367728A
CN103367728A CN2013103094824A CN201310309482A CN103367728A CN 103367728 A CN103367728 A CN 103367728A CN 2013103094824 A CN2013103094824 A CN 2013103094824A CN 201310309482 A CN201310309482 A CN 201310309482A CN 103367728 A CN103367728 A CN 103367728A
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graphite
positive electrode
source
active natural
natural graphite
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张露露
段松
杨学林
李明
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China Three Gorges University CTGU
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to an activated natural graphite modified Li2FeSiO4 cathode material and its preparation method. After activation by ball milling, natural graphite is dispersed in a precursor of lithium salt, iron source and silicon source and undergoes high temperature sintering so as to obtain the Li2FeSiO4 cathode material. Specifically, the method comprises the following steps: lithium salt, ferric salt and silicon source are mixed in an alcoholic solution and the mixture is transferred to a reflux system of 80 DEG C to carrying out reflux for 24h; the ball-milling activated natural graphite micro powder is added and dried to obtain a precursor powder; the precursor powder undergoes atmosphere sintering in a tubular furnace, the sintered precursor powder, acetylene black and polyvinylidene fluoride (PVdF) are stirred in a N-methyl 2 pyrrolidone (NMP) medium to form a slurry, the slurry is coated on aluminium foil, and drying, die trimming and die pressing are carried out to prepare the activated natural graphite modified Li2FeSiO4 cathode material. The material provided by the invention has advantages of lower cost, no pollution, simple synthesis technology, less emission of harmful gases during the synthesis process and excellent electrochemical cycle performance.

Description

Graphite modified ferric metasilicate lithium positive electrode material of a kind of active natural and preparation method thereof
Technical field
The present invention relates to graphite modified ferric metasilicate lithium positive electrode material of a kind of active natural and preparation method thereof, belong to field of electrochemical power source.
Background technology
Electrode material is one of principal element that affects performance of lithium ion battery, and wherein positive electrode has vital effect to the development in lithium ion battery future.The commercial li-ion cell positive material mainly contains at present: cobalt acid lithium (LiCoO 2), LiMn2O4 (LiMn 2O 4), ternary material (Li (NiCoMn) O 2), LiFePO4 (LiFePO 4) etc.LiCoO 2Be the earliest by business-like anode material for lithium-ion batteries, but Co toxicity is large, environmental pollution is more serious, and the Co reserves in the whole world are limited, expensive in addition, so its application has been subject to certain restriction.LiMn 2O 4Operating voltage high although (4 V), its capacity is not high, and (theoretical capacity is 148 mAh g -1, actual capacity is 120 mAh g only -1), and the cycle performance under the high temperature is poor.So LiMn 2O 4Had to small-scale application in lithium ion battery market.Ternary Li (NiCoMn) O 2The operating voltage of positive electrode excessively low (2.5 V), capacity was slightly inadequate when (about cut-ff voltage 3.4V) used on mobile phone; And cobalt resource is not only limited but also poisonous, and is expensive, also has been subject to certain restriction so it is used.In addition, LiCoO 2, LiMn 2O 4, Li (NiCoMn) O 2Also have safety issue etc. oxide-based positive electrode, namely overcharge or hot conditions under, LiCoO 2, LiMn 2O 4, Li (NiCoMn) O 2The oxygen that decompose to generate Deng oxide and the organic solvent in the electrolyte react and cause potential safety hazard.From the reported first such as Padhi in 1997 LiFePO 4Can be used for since the anode material for lithium-ion batteries LiFePO 4The advantages such as nontoxic, pollution-free because having, that security performance is good, raw material sources are extensive, low price, life-span are grown, and be known as in the world gradually one of the novel anode material of the tool potentiality that are high-energy power battery.Yet, because LiFePO 4Self structure and the conductivity that causes is low by (10 -10-10 -9S cm -1) and lithium ion diffusion slow (10 -14-10 -16Cm 2s -1) problem, cause this material when high current charge-discharge, easily to produce capacitance loss, therefore must carry out modification to it and just may be applied in the reality.Although the LiFePO after the modification 4Actual capacity under large electric current is expected to reach 160 mAh g -1, be higher than business-like LiCoO 2(140 mAh g -1), but its bulk density is relatively low, is unfavorable for the miniaturization development of battery, and is difficult to avoid various patent disputes, so LiFePO4 does not reach LiCoO so far yet 2The application scale.Yet, as the lithium ion anode material ferric metasilicate lithium of a new generation, except the advantages such as Stability Analysis of Structures with polyanion type positive electrode and fail safe height, also have the LiFePO of ratio 4The raw material resources of material are abundanter, cost is lower,, theoretical capacity (332 mAh gs more friendly to environment -1) more high advantage.Therefore, Li 2FeSiO 4Can compare LiFePO 4Have more wide market, demand also can be larger.
The lithium ion diffusion coefficient hangs down and the problem of low two aspects of conductivity but ferric metasilicate lithium has equally.At present, some main method of modifying comprise: (1) preparation nanometer ferric metasilicate lithium particle is to shorten the bang path of electric charge in particle; (2) adopt carbon to coat the conductivity that improves material; (3) improve the intrinsic conductivity of ferric metasilicate lithium material by cation doping.The effect that carbon coats depends primarily on carbon source.At present, the carbon source for the positive electrode modification mainly is organic carbon source and inorganic carbon source (carbon nano-tube, Graphene etc.).Because holding at high price of carbon nano-tube and Graphene, therefore actual what use mainly is sucrose and glucose in the organic carbon source, but the amorphous carbon that the organic carbon pyrolysis forms is not high because of degree of graphitization, improves limited to positive electrode conductivity.
Summary of the invention
The object of the present invention is to provide the graphite modified ferric metasilicate lithium positive electrode material of a kind of active natural (to be labeled as Li 2FeSiO 4/ (C+G), C, G represent respectively amorphous carbon and graphitized carbon).Related Li 2FeSiO 4/ (C+G) its synthesis material of positive electrode is lithium salts (CH 3COOLi2H 2O, LiOH), source of iron (Fe 2O 3, FeC 2O 42H 2O), silicon source (SiO 2, Si (C 2H 5O) 4) and active natural graphite.
The molal weight ratio in described lithium salts, source of iron, silicon source is 3 ~ 1.5:2 ~ 0.5:2 ~ 0.5; Active natural graphite accounts for 3 ~ 15% of lithium source, source of iron, silicon source gross mass.
The purity in described lithium salts, source of iron, silicon source is all greater than 99.5%; Active natural graphite is take natural flake graphite as raw material, and activation made the active natural graphite that includes amorphous carbon and graphitized carbon in 2 ~ 6 hours through ball milling, and wherein the purity of natural flake graphite is 99%, and granularity is 1200 orders.
The amorphous carbon that the alternative organic matter pyrolysis of active natural graphite of the present invention produces suppresses ferrous oxidation following advantage: (1) compares the organic carbon sources such as sucrose, glucose, and its cost is lower; (2) can effectively reduce organic matter pyrolysis and generate pernicious gas (such as CO 2, CO etc.) discharging; (3) graphite is that carbon source has improved Li 2FeSiO 4The degree of graphitization of middle residual carbon is conducive to further improve the conductivity of material, thereby improves the chemical property of material.
Another object of the present invention is to provide the preparation method of the graphite modified ferric metasilicate lithium positive electrode material of a kind of active natural.To be dispersed in the presoma of ferric metasilicate lithium after the activation of native graphite ball milling, then obtain ferric metasilicate lithium positive electrode material by high temperature sintering, the a part of amorphous carbon that generates in the activation process prevents that as reducing agent the ferrous iron in the raw material is oxidized, and another part graphite is the ferric metasilicate lithium grain surface that generating of high degree of dispersion then.
Concrete preparation method is for transferring to the 24h that refluxes in 80 ℃ the backflow system after lithium salts, molysite and silicon source are mixed in alcoholic solution, obtain powder after evaporating alcohol; Add the native graphite micro mist after ball milling activates, take acetone as medium ball milling 6h, obtain precursor powder after the oven dry; Precursor powder carried out nitrogen atmosphere 8 ~ 12 hours with 600 ~ 700 ℃ in tube furnace, be that 70 ~ 80:12 ~ 17:8 ~ 12 stir into slurry in mass ratio in 1-METHYLPYRROLIDONE (NMP) medium with acetylene black, Kynoar (PVdF) behind the sintering, coat on the aluminium foil, through super-dry, rush film and press mold is made the graphite modified lithium metasilicate positive electrode of active natural.
The high-performance Li of the present invention's preparation 2FeSiO 4/ (C+G) positive electrode has following distinguishing feature:
(1) cost is cheaper, and is pollution-free;
(2) synthesis technique is simple;
(3) the building-up process noxious gas emission is few;
(4) the material electrochemical cycle performance is excellent.
Description of drawings
Fig. 1 is Li among the embodiment 2 2FeSiO 4/ (C+G) X-ray diffracting spectrum of positive electrode.
Fig. 2 is Li among the embodiment 2 2FeSiO 4/ (C+G) stereoscan photograph of material, (wherein 1,2 be respectively corresponding identified areas in the stereoscan photograph can spectrogram, 2 to sentence blocky graphite be main, is attached with a certain amount of Li at graphite surface 2FeSiO 4Particle; 1 place is then with Li 2FeSiO 4Be main, Li 2FeSiO 4Particle surface is coating amorphous carbon).
Fig. 3 (a) is Li among the embodiment 2 not 2FeSiO 4/ (C+G) electrode the 1st, 2 and 10 charging/discharging voltage curves, (b) Li 2FeSiO 4/ (C+G) electrode cycle performance curve.
Embodiment
Below by the description of embodiment and comparative example, further set forth substantive distinguishing features of the present invention and advantage.For convenience of description, at first comparative example is narrated, and then described specific embodiments of the invention.
Comparative example 1
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transferring to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, is sucrose ball milling 6h in medium-acetone of 15% with the powder that obtains behind the evaporation alcohol and its mass fraction, obtains precursor powder after the oven dry.Presoma carries out nitrogen atmosphere with 650 ℃ in tube furnace, constant temperature 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 149.5 mAh g -1, discharge capacity maintains 138.2 mAh g after 50 circulations -1, capability retention is 92.4%.The specific discharge capacity of material is lower, and cyclical stability is also undesirable, and this explanation adopts the modification of organic matter pyrolysis carbon to improve limited to material electrochemical performance.
Embodiment 1
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 4 hours, the quality that wherein activates graphite accounts for 3% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 650 ℃ in tube furnace, and constant temperature keeps 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity only is 47.6 mAh g -1, discharge capacity is 16.8 mAh g after 50 circulations -1
Embodiment 2
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 4 hours, the quality that wherein activates graphite accounts for 5% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 650 ℃ in tube furnace, and constant temperature keeps 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.From the described Li of Fig. 1 2FeSiO 4/ (C+G) X-ray diffracting spectrum of positive electrode can find out that all diffraction maximums all can be corresponding to the monoclinic system ferric metasilicate lithium, and space group is P2 1/ n, diffraction maximum is sharp-pointed, shows the sample well-crystallized.Li as can see from Figure 2 2FeSiO 4/ there is in (C+G) flaky graphite to exist, nano level amorphous carbon coats the ferric metasilicate lithium particle and is attached to graphite surface, and amorphous carbon and graphite microcrystal have formed effective conducting base, to Li 2FeSiO 4Conductivity play good improvement effect.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Fig. 3 is Li 2FeSiO 4/ (C+G) the charging/discharging voltage curve of positive electrode (the 1st, 2 and 10 time) and cycle performance figure.The charging/discharging voltage scope is 1.5 ~ 4.6 V in the test process, and charge-discharge magnification is 0.1 C.Material initial charge capacity is 137.9 mAh g -1, discharge capacity is 170.3 mAh g -1, the 2nd charging capacity is 197.9 mAh g -1, discharge capacity is 168.7 mAh g -1, the 10th time charging capacity is 169.4mAh g -1, discharge capacity is 160.4 mAh g -1By figure (a) can see the 10th time of material and the 2nd voltage curve substantially overlapping, illustrative material has the cyclical stability of excellence.Can be found out by figure (b), capacity was 151.2 mAh g after material circulated through 50 times -1, capability retention is 88.7%, shows higher specific discharge capacity and good cyclical stability.
Embodiment 3
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 4 hours, the quality that wherein activates graphite accounts for 7% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 650 ℃ in tube furnace, and constant temperature keeps 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 156.7 mAh g -1, discharge capacity is 144.8 mAh g after 50 circulations -1, capability retention is 92.4%.
Embodiment 4
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 4 hours, the quality that wherein activates graphite accounts for 10% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 650 ℃ in tube furnace, and constant temperature keeps 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1MLiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 143.9 mAh g -1, discharge capacity is 135.4 mAh g after 50 circulations -1, capability retention is 94.1%.
Embodiment 5
With CH 3COOLi2H 2O, FeC 2O 42H 2O and Si (C 2H 5O) 4Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 2:1:1, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 4 hours, the quality that wherein activates graphite accounts for 15% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 650 ℃ in tube furnace, and constant temperature keeps 10h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 110.7 mAh g -1, discharge capacity is 109 mAh g after 50 circulations -1, capability retention is 98.46%.
Embodiment 6
With LiOH, Fe 2O 3And SiO 2Transfer to the 24h that refluxes in 80 ℃ the backflow system after mixing in alcoholic solution take mol ratio as 1.5:0.5:0.5, obtain powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 2 hours, the quality that wherein activates graphite accounts for 5% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 600 ℃ in tube furnace, and constant temperature keeps 8h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 163.8 mAh g -1, discharge capacity is 141.2 mAh g after 50 circulations -1, capability retention is 86.2%.
Embodiment 7
With LiOH, Fe 2O 3And SiO 2Mol ratio is to transfer to the 24h that refluxes in 80 ℃ the backflow system after 3:2:2 mixes in alcoholic solution, obtains powder behind the evaporation alcohol.Add the native graphite micro mist of ball milling activation after 6 hours, the quality that wherein activates graphite accounts for 5% of gross mass, take acetone as medium ball milling 6h, obtains precursor powder after the oven dry.Presoma carries out the nitrogen atmosphere sintering with 700 ℃ in tube furnace, and constant temperature keeps 12h, the active material powder that obtains sieves and presses mass ratio furnishing slurry in 1-METHYLPYRROLIDONE (NMP) medium of 75:15:10 behind 200 orders with acetylene black, Kynoar (PVdF), coat on the aluminium foil, through super-dry, rush film and press mold is made work electrode.Take metallic lithium foil as to electrode, polypropylene screen is barrier film, 1M LiPF 6/ (EC+DMC) (1:1) carry out constant current charge-discharge test for electrolyte is assembled into battery, voltage range is between 1.5 ~ 4.6V.Material 0.1C first discharge capacity is 142.7mAhg -1, discharge capacity is 123.8mAhg after 50 circulations -1, capability retention is 84.1%.

Claims (7)

1. graphite modified lithium metasilicate positive electrode of active natural, it is characterized in that: these raw material comprise lithium salts, source of iron, silicon source, wherein lithium salts is CH 3COOLi2H 2O or LiOH, source of iron is Fe 2O 3Or FeC 2O 42H 2O, the silicon source is SiO 2Or Si (C 2H 5O) 4, described raw material also comprise active natural graphite.
2. the graphite modified lithium metasilicate positive electrode of active natural according to claim 1, it is characterized in that: the mol ratio in lithium salts, source of iron, silicon source is 3 ~ 1.5:2 ~ 0.5:2 ~ 0.5.
3. the graphite modified lithium metasilicate positive electrode of active natural according to claim 1 is characterized in that: active natural graphite accounts for 3 ~ 15% of lithium source, source of iron, silicon source gross mass.
4. the graphite modified lithium metasilicate positive electrode of active natural according to claim 1, it is characterized in that: the purity in lithium salts, source of iron, silicon source is all greater than 99.5%.
5. the graphite modified lithium metasilicate positive electrode of active natural according to claim 1, it is characterized in that: active natural graphite is as raw material take natural flake graphite, activation made the active natural graphite that includes amorphous carbon and graphitized carbon in 2 ~ 6 hours through ball milling, wherein the purity of natural flake graphite is 99%, and granularity was 1200 orders.
6. method for preparing the graphite modified lithium metasilicate positive electrode of active natural is characterized in that: transfer to the 24h that refluxes in 80 ℃ the backflow system after 1) lithium salts, molysite and silicon source being mixed in alcoholic solution, obtain powder behind the evaporation alcohol; 2) the native graphite micro mist after the activation of adding ball milling take acetone as medium ball milling 6h, obtains precursor powder after the oven dry; 3) to carry out in tube furnace behind the atmosphere sintering with acetylene black, Kynoar (PVdF) be that 70 ~ 80:12 ~ 17:8 ~ 12 stir into slurry in 1-METHYLPYRROLIDONE (NMP) medium to precursor powder in mass ratio, coat on the aluminium foil, through super-dry, rush film and press mold is made the graphite modified lithium metasilicate positive electrode of active natural.
7. the method for preparing the graphite modified lithium metasilicate positive electrode of active natural according to claim 6 is characterized in that: in the step 3) in nitrogen atmosphere with 600 ~ 700 ℃ of sintering 8 ~ 12 hours.
CN2013103094824A 2013-07-23 2013-07-23 Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method Pending CN103367728A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110495026A (en) * 2017-03-30 2019-11-22 松下知识产权经营株式会社 Negative electrode material and non-aqueous electrolyte secondary battery
CN111224083A (en) * 2019-12-03 2020-06-02 珠海中科兆盈丰新材料科技有限公司 Graphite/silicate composite material and preparation method thereof
CN113937283A (en) * 2021-10-27 2022-01-14 苏州中材非金属矿工业设计研究院有限公司 Modified spherical graphite negative electrode material and preparation method and application thereof
CN114883553A (en) * 2022-05-11 2022-08-09 兰州理工大学 Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C

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CN102013490A (en) * 2010-11-02 2011-04-13 三峡大学 High rate lithium iron phosphate anode material and preparation method thereof
CN102723488A (en) * 2012-06-22 2012-10-10 三峡大学 High-rate performance vanadium-doped lithium iron silicate anode material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN102013490A (en) * 2010-11-02 2011-04-13 三峡大学 High rate lithium iron phosphate anode material and preparation method thereof
CN102723488A (en) * 2012-06-22 2012-10-10 三峡大学 High-rate performance vanadium-doped lithium iron silicate anode material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110495026A (en) * 2017-03-30 2019-11-22 松下知识产权经营株式会社 Negative electrode material and non-aqueous electrolyte secondary battery
CN110495026B (en) * 2017-03-30 2022-07-15 松下知识产权经营株式会社 Negative electrode material and nonaqueous electrolyte secondary battery
CN111224083A (en) * 2019-12-03 2020-06-02 珠海中科兆盈丰新材料科技有限公司 Graphite/silicate composite material and preparation method thereof
CN111224083B (en) * 2019-12-03 2021-05-14 珠海中科兆盈丰新材料科技有限公司 Graphite/silicate composite material and preparation method thereof
CN113937283A (en) * 2021-10-27 2022-01-14 苏州中材非金属矿工业设计研究院有限公司 Modified spherical graphite negative electrode material and preparation method and application thereof
CN114883553A (en) * 2022-05-11 2022-08-09 兰州理工大学 Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C
CN114883553B (en) * 2022-05-11 2023-07-18 兰州理工大学 Alkaline solution selective corrosion preparation of porous nano Li 2 FeSiO 4 Method of/C

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Application publication date: 20131023