CN106654239B - A kind of interior carbon dope lithium ion battery material and preparation method thereof - Google Patents
A kind of interior carbon dope lithium ion battery material and preparation method thereof Download PDFInfo
- Publication number
- CN106654239B CN106654239B CN201710115761.5A CN201710115761A CN106654239B CN 106654239 B CN106654239 B CN 106654239B CN 201710115761 A CN201710115761 A CN 201710115761A CN 106654239 B CN106654239 B CN 106654239B
- Authority
- CN
- China
- Prior art keywords
- carbon
- source
- transition metal
- lithium
- initial soln
- 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.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of interior carbon dope lithium ion battery materials and preparation method thereof; material includes the phosphate containing lithium and transition metal; carbon dope in the phosphate crystal containing lithium and transition metal; outer cladding carbon; method is inert gas to be passed through after mixing using the phosphorus source with carbon-based group or the transition metal source with carbon-based group with deionized water or reducibility gas, addition protective agent prepare the phosphatic presoma containing lithium and transition metal; then by organic carbon source mixing and calcination process, our final product is finally obtained.Wherein organic carbon source is coated on the phosphate crystal surface containing lithium and transition metal as exterior carbon, and the carbon after the phosphorus source with carbon-based group or the transition metal source decomposition with carbon-based group is present in crystal as internal carbon.The compound finally prepared illustrate it special appearance structure and excellent chemical property.Most importantly, which has shown the excellent properties for surmounting LFP theoretical capacity.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of lithium ion battery material and preparation method thereof.
Background technique
Nowadays, whole world more and more people pay close attention to electric car (EVs), hybrid electric automobile (HEVs) and insert
Enter formula hybrid electric automobile (PEVs), they are equipped with the lithium ion battery (LIBs) of high capacity and high-energy.As most
Has one kind of the LIBs positive electrode of potentiality, the LiFePO4 (LFP) of olivine structural is for the first time in 1997 by Goodenough
It proposes, since its extensive and powerful application has been instantly available extensive concern.It is reported that LFP is as LIBs positive electrode
Higher with many important advantages, including capacity, security performance is high, and stability is high, acceptable operating voltage (3.4 V
vs. Li+/ Li), environment compatibility is good and cheap.
But with other common lithium ion battery (LIBs) positive electrodes comparatively, the theoretical capacity of LFP is relatively low
(170 mA h g-1) and also relatively low (the 1.1-1.3 g mL of tap density-1), which results in the volume energy densities of LFP simultaneously
Not high (600 W h L-1), and in the development process of LFP, there is still a need for further change the transmission problem of lithium ion and electronics
It is kind.Since ionic mobility is low, some lithium ions directionally cannot completely disengage out from olivine structural, this will lead to one
The loss of a little capacity, and then cause commercialized LFP capacity lower (lower than 150 m Ah g-1).Therefore, LFP is only answered mostly
With on fixed energy storage, such as renewable energy, smart grid and vehicle-mounted electric energy storage (HEVs, EVs and PEVs),
And using seldom in Portable electronic equipment.
Cobalt acid lithium (LiCoO2) it is widely used in portable device, such as mobile phone, computer and camera.LiCoO2It is main excellent
Gesture is volume energy density height (1200 W h L-1), this has benefited from its high tap density (2.2 g mL-1), this is almost quotient
Two multiple values of industry LFP.But LiCoO2Greatest problem be that capacity attenuation is serious, which results in LiCoO2Cycle-index only
Have 500 or so.Therefore, commercialized LiCoO2It is faced with service life short problem.
Recently, more and more biological materials, which are applied to, prepares lithium ion cell positive and negative electrode material, this is main
It is to have environment friendly due to biological material, storage capacity is enriched and sustainability.Carbon source inside biological material is past
It is past to will affect the last pattern of material and performance.Phytic acid (PhyA) { chemical formula C6H6(H2PO4)6, with phytic acid or flesh
The phosphatic form of alcohol six is widely known, and is also the principal mode of storage phosphorus.Phytic acid is primarily present in beans, including big
Beans and corn, it is a kind of naturally occurring non-toxic organic macromolecular compound.But as a kind of anti-nutritional factors, phytic acid limit
Application of the beans in food and feed is made.Therefore, the separation and use of phytic acid are particularly important.Phytate molecule contains
6 carbon atoms and 6 phosphate groups.The special construction of phytic acid causes it that can charge cation generation chelating work with many multivalence
With, such as Fe2+, Fe3+, Ca2+, Mg2+, and Zn2+, this is because the very strong electronegativity in phytic acid surface.The chelating that they are formed
Object is soluble in acid condition and precipitates in neutral conditions.
Useful phytic acid is prepared for carbon-coated LiFePO4 (LiFePO in the prior art4/ C), his concrete scheme is:
Step 1: phytic acid and LiOH to be first dissolved in the clear solution for forming brown color in deionized water, it is being stirred continuously
Under conditions of FeSO is added4, phytic acid/FeSO4/ LiOH is 1:6:18, and the ratio of Li/Fe/P is 3:1:1 in solution；
Step 2: being bubbled half an hour with nitrogen；
Step 3: solution being quickly transferred in the reaction kettle of stainless steel after the completion of being bubbled, being warming up to 180 DEG C and protect
Room temperature is naturally cooled to after holding 6 hours；
Step 4: sediment is collected by centrifugation out, washed repeatedly with deionized water and ethyl alcohol, finally in 60 DEG C of dry 8h；
Step 5: above-mentioned drying material is heated to 675 DEG C in tube furnace, and it is passed through containing 95% argon gas and 5% hydrogen
The mixed gas of gas keeps the temperature 12 hours.
Step 6: the acetylene gas that purity is 50% is introduced into above-mentioned tube furnace, Ventilation Rate is 30 cm3 min-1,
Room temperature is cooled to after ventilation half an hour.
This method is to be prepared for carbon-coated LiFePO4 LiFePO with phytic acid4/ C, the material prepared is in 1 C
Capacity is only 120 mA h g under (coulomb)-1, 0.1 C(coulombs) and it is only 140-160 mA h g-1, most well below other
The performance for the LiFePO4 that number is prepared.Its reason is: 1, without adjusting the final pH of solution.Since phytic acid is ten binary
Acid, and be thick liquid, which results in phytic acid rapidly and sufficiently to dissolve and react as phosphoric acid.In the ratio of this method
The pH of the lower final solution of example is stronger alkaline (10.2-11.8), this easily leads to Fe2+It is oxidized to Fe in aqueous solution3+,
Lead to Li in final material+Content wretched insufficiency cause capacity be greatly reduced；2, due to 675 DEG C of its calcination temperature, calcining temperature
Not enough, phytic acid decomposition is not thorough degree, is caused the interior carbon dope that can store additional lithium ion that could not be formed well, is not played plant
The maximum advantage of acid；3, calcination time it is too long cause LFP crystal further increase and crystal grain reunite it is serious, cause in
Carbon dope is difficult to enter into LFP crystal and influences final structure and performance；4, since phytic acid is ten binary acid, phytic acid and
FeSO4Reaction be not so good as phosphoric acid and FeSO4Reaction speed it is fast, first use LiOH and phytic acid hybrid reaction, add FeSO4, this meeting
Result in Fe2+It not can be carried out with phytic acid and fully react in the early stage, while also increasing Fe2+The risk being oxidized, this will necessarily
The ingredient for influencing final product causes capacity relatively low；5, protective agent is not added in hydro-thermal reaction, can not effectively hinder
Fe2+Oxidation, this would necessarily affect the ingredient of final product, cause capacity relatively low.Generally speaking, this method is main still
Enough interior carbon dopes could not be accessed, and structure to LFP material and performance play apparent improvement result and Fe2+Easily
Being oxidized leads to Li+Content deficiency is to cause energy loss.The material is eventually led at 1 C(coulombs) under capacity be only 120
mA h g-1, 0.1 C(coulombs) and it is only 140-160 mA h g-1。
In the prior art also by electrochemical stripping thin graphene (EG piece), then by itself and commercialized ferric phosphate
Lithium material is compounded to form the LiFePO4 (cLFP) of thin graphene cladding, then reacts by 180 DEG C of hydro-thermal reaction, finally group
Dress up battery.Although the cLFP that the technology obtains is at 0.1 C(coulombs) under capacity reached 208 mA h g-1, but he institute
The graphene used is but very expensive material, high production cost, in the large-scale production for being currently unfavorable for material.
In conclusion being had following defects that using the LiFePO 4 material that above two method prepares
1, the carbon-coated LiFePO 4 for lithium ion batteries (LiFePO prepared using phytic acid4/ C) material is at 0.1 C(coulombs) be only
140-160 mA h g-1, serious theoretical capacity (the 170 mA h g for being lower than LiFePO4-1), large-scale industry can not be applied to
Metaplasia produces.
2, thin graphene cladding LiFePO4 (cLFP) although at 0.1 C(coulombs) under capacity reached 208 mA
h g-1, but graphene used in him is but very expensive material, high production cost is currently being unfavorable for the big of material
Large-scale production.
In conclusion the shortcomings that above-mentioned lithium ion battery material respectively has oneself, at present there is no one kind have both above-mentioned lithium from
Therefore the lithium ion battery material of sub- all advantages of battery material develops that a kind of capacity is high, tap density is high, service life
Long and low production cost lithium ion battery material is very necessary.
Summary of the invention
In order to overcome respective defect existing for above-mentioned existing lithium ion battery material, the present invention provides a kind of interior carbon dopes
Lithium ion battery material, the lithium ion battery material have high capacity, tap density height, long service life and production cost low
Advantage.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon.
In the interior carbon dope lithium ion battery material, the molar ratio of lithium, transition metal and P elements are as follows: lithium: transition metal:
Phosphorus=(1.1~1.9): 1:(0.8~1.2).
The present invention also provides a kind of method for preparing above-mentioned interior carbon dope lithium ion battery material, what this method prepared
Interior carbon dope lithium ion battery material capacity under low range can be more than the theoretical capacity of LiFePO4, and tap density is high, uses
Service life is long, and does not have to graphene-coated lithium iron phosphate, and production cost is low, is conducive to large-scale popularization and application, and this method is specific
Are as follows:
Step 1, phosphorus source, water-soluble transition metal source, deionized water and water-soluble lithium source with carbon-based group are mixed molten
Solution forms initial soln I；Or by transition metal source, water-soluble phosphorus source, deionized water and water-soluble lithium source with carbon-based group
Mixed dissolution forms initial soln II；Or by the mixing of the phosphorus source with carbon-based group and the transition metal source with carbon-based group
Object, deionized water and water-soluble lithium source mixed dissolution form initial soln III；Or by the phosphorus source with carbon-based group and there is carbon
The mixture of the transition metal source of group, the water-soluble phosphorus source of phosphorus source without carbon-based group or the water solubility without carbon-based group
Transition metal source, deionized water and water-soluble lithium source mixed dissolution form initial soln IV；
Step 2, the pH value of initial soln I in regulating step 1, initial soln II, initial soln III and initial soln IV is extremely
After 5.5-10.5,0.5-2 h is reacted；
Step 3, after the solution after step 2 being heated to 180-240 DEG C, 1-12 h is reacted；
Step 4, by after step 3 processing obtained material be washed with deionized water 0-2 times, then wash 1 time with ethyl alcohol, so
After be centrifuged, washing and alcohol wash when, the deionized water of addition and the amount of alcohol will guarantee material in deionized water and alcohol
In concentration be 0.01-0.15 g mL-1；
Step 5, dry by step 4 treated material；
Step 6, carbon source is mixed into the material after step 5 processing；
Step 7, by by step 6 treated material inert gas, reducibility gas or both mixed gas
It is calcined under atmosphere, calcination temperature are as follows: 700-900 DEG C, calcination time are as follows: 1-6 h.
In step 1, lithium in the initial soln I, initial soln II, initial soln III and initial soln IV: transition gold
Belong to: the molar ratio of phosphorus=(2-4): (0.5-1.5): (0.5-1.5).
Protective agent is also added in initial soln I, initial soln II, initial soln III and initial soln IV in step 1, protects
Shield agent is ethylene glycol, glycerine or combination object.
Deionized water and protectant body in the initial soln I, initial soln II, initial soln III and initial soln IV
Product ratio is (0.5-5): 1.
Step 1 is passed through the mixing of inert gas, reducibility gas or inert gas and reducibility gas into step 2
Gas, Ventilation Rate are 100-250 cm3 min-1, preferably Ventilation Rate is 150-180 cm3 min-1。
Step 1 needs to be stirred with magnetic stirring apparatus into step 2.
Phosphorus source in step 1 with carbon-based group is phytic acid or phytate, and phytate is sodium phytate, POTASSIUM PHYTATE, phytic acid calcium
One of equal salt are a variety of.
Transition metal source in step 1 with carbon-based group is the iron containing carbon-based group, cobalt, manganese and nickel source metal.
In step 1 water-soluble transition metal source be source of iron be watersoluble divalent source of iron, water-soluble cobalt source, water-soluble manganese source or
Ferrous sulfate, frerrous chloride, ferrous bromide, ferrous nitrate, acetic acid Asia may be selected in water-soluble nickel source, such as watersoluble divalent source of iron
One of iron is a variety of, and the watersoluble divalent source of iron needs of addition are sufficiently dissolved into solution.
In step 1, water-soluble lithium source is selected in lithium hydroxide, lithium acetate, lithium bromide, lithium chloride, lithium iodide and lithium nitrate
It is one or more, need to be slowly added dropwise in the solution in step 3, sufficiently be reacted.
In step 2, pass through the pH value of addition phytic acid or lithium hydroxide adjusting solution to 6.8-7.2,2 h of solution reaction.
In step 3, after the solution after step 2 is quickly transferred in reaction kettle, solution is heated by reaction kettle
To after 180-240 DEG C, 1-12 h is reacted.
In step 3, after the solution after step 2 is quickly transferred in reaction kettle, first it is passed through into reaction kettle lazy
The mixed gas of property gas, reducibility gas or both, at least ventilates after five minutes, closes the air inlet and outlet of reaction kettle
Mouthful, after reaction kettle is then warming up to 180-240 DEG C again, react 1-12 h.
In step 3, reaction kettle selects high-temperature high-pressure reaction kettle, and with magnetic stirrer, high after 10 min that ventilate
After warm autoclave is warming up to 200 DEG C, 2-3h is reacted.
In step 5, drying temperature is at 60 DEG C -120 DEG C, and drying time is 8-24 h, using vacuum drying mode
It is dried, preferably 80 DEG C of drying temperature, drying time preferably 12 h.
In step 6, the amount of the carbon source of incorporation is the 5%-30% by step 5 treated material weight.
In step 6, carbon source is organic carbon source, such as glucose, sucrose, lactose, maltose, phenolic resin, epoxy resin, is gathered
Ethylene glycol or inorganic carbon source, such as acetylene gas, the amount of carbon source incorporation preferably pass through the 10% of the material weight of step 5.
It is additionally provided with cold pressing step between step 6 and step 7, disk, disk is made in the material cold pressing that step 6 obtains
Shape material radius is 0.5-10 cm, and with a thickness of 0.5-12 mm, preferably disc-shaped material radius is 2-4 cm, with a thickness of 2-4
mm。
In step 7, calcination temperature is 750 DEG C, calcination time 2-3h.
Compared with the existing technology, the present invention there are following the utility model has the advantages that
1, interior carbon dope lithium ion battery material provided by the invention, it is special including the phosphate containing lithium and transition metal
Sign is: carbon dope in the phosphate crystal containing lithium and transition metal, outer cladding carbon.The interior carbon dope lithium ion battery material
In material, the molar ratio of lithium, transition metal and P elements are as follows: lithium: transition metal: phosphorus=(1.1~1.9): 1:(0.8~1.2).By
In carbon dope in the phosphate crystal containing lithium and transition metal, and has on interior carbon dope and can carry out reversible oxidation with lithium ion
The oxygen-containing functional group of reduction reaction significantly improves the phosphatic capacity containing lithium and transition metal, and capacity can in 0.1 C
To reach 218 mA h g-1, far beyond LFP theoretical capacity value (170 mA h g-1), due to containing lithium and transition metal
Phosphate crystal outer cladding carbon, improve the electric conductivity of LiFePO4, this is also beneficial to provided by the invention containing lithium and mistake
Cross the theoretical capacity that the phosphatic capacity of metal can be more than LFP in low range.
2, the present invention also provides the preparation method of interior carbon dope lithium ion battery material, it is initial that this method increases adjusting
Solution I, initial soln II, initial soln III and initial soln IV pH value to 5.5-10.5 after, the step of reacting 0.5-2 h,
If pH value is excessively high, transition metal ions is very easy to be oxidized in aqueous solution, leads to Li in final material+Content it is insufficient
Cause capacitance loss；PH value is too low, and for the phosphate material containing lithium and transition metal of formation in acid condition, meeting part is molten
Solution, also will affect the last formation of material.Thus pH value is too low or too high can all influence containing lithium and transition metal
Phosphatic growth, it is necessary to which control does not control pH in background technique in 5.5-10.5, if according to background skill
Reagent is added in ratio in art, and pH will be excessively high, and it is exactly to be oxidized because of the inside section transitions metal ion that its capacity is very low,
Lead to wherein Li+It is lower to have eventually led to its capacity for content wretched insufficiency；3. the present invention is first to mix organic carbon source, carbon is formed
Tube furnace calcining is carried out again after cladding, such to be advantageous in that, exterior carbon can fully be coated on the surface of LiFePO4,
So as to improve the electric conductivity of material.Calcination time is 1-6 h at 4. temperature of the present invention in calcining is 700-900 DEG C,
For with respect to the background art, calcination temperature is higher, and calcination time is less, and is increased to 700 DEG C just because of calcination temperature,
So that the phosphorus source with carbon-based group and the transition metal source complete decomposition with carbon-based group, guarantee to store additional lithium ion
Interior carbon dope is formed in well in the phosphate crystal containing lithium and transition metal, plays the maximum advantage of phytic acid, and is calcined
Time shortens to 6h or less, it will be able to effectively avoid containing the growth of the phosphate crystal of lithium and transition metal and crystal grain group
It is poly-, guarantee in carbon dope be able to enter in the phosphate crystal crystal containing lithium and transition metal, ultimately form outer cladding carbon and
The phosphoric acid material containing lithium and transition metal of interior carbon dope, and the capacity under low range is made to be more than that the theoretical of LiFePO4 holds
Amount；5, the material that in the present invention, step 3 obtains is washed with deionized water 0-2 times, then is washed 1 time with ethyl alcohol, then carries out at centrifugation
Reason, when washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material that step 3 obtains in deionized water and alcohol
Concentration be 0.01-0.15 g mL-1；If repeatedly washing or alcohol are washed, it will what is needed on the last interior carbon dope of material
Additional lithium ion is washed off, so that influencing the final performance of material will not be especially high.In addition can also wash off it is additional have it is carbon-based
The phosphorus source and transition metal source with carbon-based group of group, and exactly these additional phosphorus sources with carbon-based group and with carbon-based group
Transition metal source will form last interior carbon dope in calcination process, if additional has carbon-based group in washing process
Phosphorus source and transition metal source with carbon-based group be washed off, will lead to the presence for not having enough interior carbon dopes in final material,
To which position can not be provided for additional lithium ion, so that additional capacity cannot be provided.It can guarantee and finally obtained enough in this way
Interior carbon dope can carry out reversible redox reaction with lithium ion, to show the performance of ultra-high capacity.
3, the present invention is anti-after protectant protection, divalent source of iron are reacted with phytic acid, adjust pH value 5.5-10.5
Answer 0.5-2 h, first mix outer carbon after calcine again and calcination temperature control is at 700-900 DEG C, calcination time control is in 6h hereinafter,
So that the final product for finally obtaining us forms the special construction of outer cladding carbon and interior carbon dope, organic carbon source is as external
The carbon source (GC) of incorporation is coated on the phosphorus source on the phosphate surface containing lithium and transition metal, with carbon-based group or has carbon
Carbon after the transition metal source of group is decomposed is present in the phosphate crystal containing lithium and transition metal as interior carbon source (IC)
It is interior.The compound finally prepared illustrate it special appearance structure and excellent chemical property.Most attach most importance to
It wants, compound presents the excellent properties for surmounting LFP theoretical capacity.And exactly this IC is provided to the material in the present invention
Additional capacity, so that the capacity of material can achieve 218 mA h g in 0.1 C-1, far beyond LFP theoretical capacity value
(170 m Ah g-1).
4, the present invention makes material tap density can achieve 1.5 g mL by way of cold pressing film-making calcining-1.Simultaneously
Transition metal ions can also be prevented to be oxidized, be conducive to the formation of end product, in the feelings for having high capacity and high-tap density
Under condition, the volume energy density of GC/IC/LFP also can achieve 1200 WhL-1.Considerably beyond conventional commercial LFP(600 W h
L-1), the volume energy density of material can match in excellence or beauty LiCoO2.In addition, the service life of commercialization LFP can achieve 2000 circles or more, this
A little considerably beyond LiCoO2.Accordingly, it is considered to which to highly-safe, volume energy density height and long service life have very
Big potentiality become the candidate materials of some portable devices.The present invention, as outer cladding carbon, has carbon using organic carbon source
The phosphorus source of group or the carbon of the transition metal source offer with carbon-based group are as interior carbon dope, relative to existing with graphene packet
For covering, production cost is substantially reduced, and is conducive to large-scale production.
5, it in step 3, after the solution after step 2 is quickly transferred in reaction kettle, is first passed through into reaction kettle
The mixed gas of inert gas, reducibility gas or both is at least ventilated after five minutes, is closed the air inlet of reaction kettle and is gone out
Port after reaction kettle is then warming up to 180-240 DEG C again, reacts 1-12 h.Be passed through inert gas, reducibility gas or
The purpose of the mixed gas of the two is the oxygen being discharged in reaction kettle, and transition metal ions is prevented to be oxidized by oxygen, and step 1
To the mixed gas for being passed through inert gas, reducibility gas or inert gas and reducibility gas in step 2, also for anti-
Only transition metal ions is oxidized by oxygen.
Detailed description of the invention
Fig. 1 is GC/IC/LFP structural schematic diagram；
Fig. 2 a is the XRD(X x ray diffraction of GC/LFP and GC/IC/LFP) figure；
Fig. 2 b is part diffraction maximum partial enlarged view in Fig. 2 a；
Fig. 2 c is the HRTEM(high resolution TEM of GC/IC/LFP) figure；
The HRTEM that Fig. 2 d is GC/LFP schemes；
Fig. 3 is the phase between low frequency section, the impedance of GC/LFP and GC/IC/LFP and the negative half power of angular frequency
The variation and matched curve figure answered；
Fig. 4 is the XP SC1s(X X-ray photoelectron spectroscopy X carbon 1s open score of IC) spectrogram；
Fig. 5 is SiO2, GC/SiO2And IC/SiO2Cyclic voltammogram, sweep speed be 1 mV s-1；
Fig. 6 is the charging and discharging curve of GC/IC/LFP under 0.1 C；
Fig. 7 a be C/LFP/ECGO(electrochemical stripping graphite oxide) and GC/IC/LFP charging and discharging curve figure；
Fig. 7 b is the differential curve figure made to the curve in Fig. 7 a；
Fig. 7 c is SiO2, GC/SiO2And IC/SiO2Charging and discharging curve figure；
Fig. 7 d is to IC/SiO in Fig. 7 c2The differential curve figure that curve is made；
Fig. 8 is the cyclic voltammogram of GC/LFP and GC/IC/LFP, sweeps 0.1 mV s-1 of speed；
Fig. 9 a is that the SEM of GC/IC/LFP presoma schemes；
Fig. 9 b is that the TEM of GC/IC/LFP presoma schemes；
The SEM that Fig. 9 c is GC/IC/LFP schemes；
The TEM that Fig. 9 d is GC/IC/LFP schemes；
The SEM that Fig. 9 e is GC/LFP schemes；
The TEM that Fig. 9 f is GC/LFP schemes；
Figure 10 is constituent content contrast table in GC/IC/LFP of the present invention and existing GC/LFP.
Specific embodiment
The principle of the present invention are as follows:
The interior carbon IC of phytic acid preparation can be deep into LFP intracell (Fig. 1), so that the lattice parameter of LFP obtains centainly
The increase (Fig. 2) of degree, such as the position of diffraction maximum move to left the growth of (Fig. 2 b) and spacing of lattice (Fig. 2 d are common phosphoric acid
The GC/LFP of preparation；The GC/IC/LFP that Fig. 2 c is prepared for our phytic acid).Above-mentioned factor is beneficial to promote lithium ion in LFP
It spreads (Fig. 3), and then improves the performance of LFP.Two kinds of materials are in the region Warburg (low-frequency range region) interior slope in comparison diagram 3
It can be seen that GC/IC/LFP has higher lithium ion diffusion constant (D) in the application.
Many oxygen-containing functional groups (Fig. 4) is rich on the interior carbon IC of phytic acid preparation.For carbon material, the oxygen-containing functionalization base in surface
The introducing of group is a kind of effective ways for improving material energy densities.Oxygen atom in this carbonyl or other oxygen-containing groups is past
Toward the marginal position combined in carbon.This oxygen-containing functionalization group in surface can undergo reversible faraday's reaction, this feature
Property faraday's reaction peak tend to occur at 3.0 V and 3.4 V nearby (vs. Li+/ Li).The redox reaction can indicate
It is as follows :-C=O+Li+ + e-↔ -C-OLi.It the position of the redox peaks of oxygen-containing group can be because of the form and carbon of carbon
Content it is different and change.IC with abundant oxygen-containing functional group also has features described above (Fig. 5), its redox peaks
About 3.3 V and 3.5 V are appeared in, and the GC of glucose preparation leads to apparent oxygen do not occur due to lacking oxygen-containing functional group
Change reduction peak.
Exactly these IC rich in oxygen-containing functional group provide storage location to more lithium ions, lead to GC/IC/LFP
Middle lithium ion content is higher (Figure 10), compared element in the GC/IC/LFP in the application and conventional GC/LFP in Figure 10 and contains
The comparison of amount.And exactly this IC provides additional capacity to the material GC/IC/LFP in the application, leads to the capacity of material
It can achieve 218 mA h g in 0.1 C-1(Fig. 6), far beyond LFP theoretical capacity value (170 mA h g-1).
Corresponding result can also be obtained by carrying out differential process to the charging and discharging curve of material.Fig. 7 b is filled in Fig. 7 a
The differential curve of discharge curve, it can be seen that common GC/LFP only has a pair of of peak, illustrates that its capacity is just derived from LFP sheet
Body.But the GC/IC/LFP in the application possesses two pairs of peaks, other than the main peak of LFP, there are also a pair of of secondary peaks, and this is to secondary peak
Voltage location just the position of the redox peaks of IC is consistent near 3.34 V and 3.49 V and in Fig. 5.Illustrate that this is right
Secondary peak is exactly the redox peaks of IC, and exactly IC provides additional capacity causes GC/IC/LFP to possess much to surmount theory
The excellent properties of capacity.In addition, individually the charging and discharging curve of test IC and corresponding differential curve also can be demonstrate,proved similarly
Bright (Fig. 7 c and 7d).This above-mentioned mechanism for more demonstrating the application is explained.
GC/IC/LFP and conventional GC/LFP to the application are only done cyclic voltammetry (Fig. 8), and it can be seen that
GC/IC/LFP possesses two pairs of redox peaks, and area is also bigger than GC/LFP, it was demonstrated that the capacity of GC/IC/LFP compares really
GC/LFP is bigger.
Structure feature:
The pattern and structure of GC/IC/LFP and GC/LFP is characterized by SEM and TEM.Fig. 9 a is GC/ after hydro-thermal reaction
The presoma (being exactly the substance before GC/IC/LFP is not calcined) of IC/LFP.Crystal at this time shows about 1 μm of radius ellipse
Sphere, each spheroid are made of the nanocrystal of a large amount of drug sheet (50 nm or so).These fine crystal have
It arranges to sequence assembling and forms big crystal.As shown in figure 9b, the crystal of GC/IC/LFP presoma shows the sheet of square
Structure, these crystal appropriately arrange in an orderly manner.But after calcining, compared to presoma, GC/IC/LFP structure and pattern hair
It has given birth to and has thoroughly changed.As is shown in fig. 9 c, calcined material becomes unordered and clusters round bulk crystals together.These institute
The phosphate of formation shows the bulk crystals having edges and corners, and it is different that this, which is with the GC/LFP crystal for using phosphoric acid to prepare,
(Fig. 9 e) because conventional GC/LFP crystal is smooth mellow and full.Fig. 9 c shows that our bulk crystals size about exists
Between 100 to 300 nm.In addition, IC could not observe (Fig. 9 d) by SEM in IC/LFP.In conclusion IC piece is from phytate
In separate and be then present between LFP crystal, and GC is coated on except LFP crystal (Fig. 9 f).
The present invention will be further described with reference to the examples below, and described embodiment is only present invention a part
Embodiment is not whole embodiment.Based on the embodiments of the present invention, those skilled in the art are not making
Other embodiments used obtained, belong to protection scope of the present invention under the premise of creative work.
Embodiment 1
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour iron lithium, the weight ratio of lithium, iron and P elements in the interior carbon dope lithium ion battery material are as follows: Li:Fe:P=1.1:1:1.08.
The interior carbon dope lithium ion battery material of the embodiment the preparation method comprises the following steps: including the following steps:
Step 1, phytic acid (phosphorus source with carbon-based group) is mixed with deionized water, is passed through argon gas, Ventilation Rate 100
cm3 min-1, while with magnetic stirrer solution；
Step 2, it by ferrous sulfate, is added in the solution in step 1 and dissolves；
Step 3, it will be dissolved in the solution in ethylene glycol addition step 2；
Step 4, lithium hydroxide is dissolved into water, is then added in the solution in step 3, is reacted, formed initial
Solution, initial soln need to meet following require: lithium: iron: the body of water and ethylene glycol in the molar ratio of phosphorus=2:1.5:0.5 solution
Product ratio is 0.5:1.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
5.5, allow 0.5 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reaction kettle liter with argon gas, 10 min rear enclosed air inlet and air outlet of ventilation are passed through
Temperature reacts 10 h to after 180 DEG C；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, alcohol is washed 1 time, then carries out centrifugal treating, and when alcohol is washed, the amount that alcohol is added will guarantee the material that step 7 obtains
Expect that the concentration in alcohol is 0.01 g mL-1；
Step 9, by the material being collected at 120 DEG C, 8 h are dried in vacuo；
Step 10, it is uniformly mixed after mixing glucose, the weight of the glucose of incorporation is by step 9 treated material
Expect the 5% of weight；
Step 11, the material Jing Guo step 10 being carried out being cold-pressed into disk, disc-shaped material radius is 0.5cm, with a thickness of
0.5 mm；
Step 12, the disk material after cold pressing is placed in tube furnace, is passed through high-purity argon gas, calcine 6 at 700 DEG C
h。
After above-mentioned steps are handled, the LiFePO4 material of the outer carbon coating and interior carbon dope that are prepared by glucose has just been obtained
Material, capacity is (202 mA h g at 0.1C-1).
Embodiment 2
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour manganese lithium, the weight ratio of lithium, manganese and P elements in the interior carbon dope lithium ion battery material are as follows: lithium: manganese: phosphorus=1.9:1:0.8.
The preparation method of the embodiment, characterized by the following steps:
Step 1, sodium phytate (phosphorus source with carbon-based group) is mixed with deionized water, is passed through helium, Ventilation Rate 150
cm3 min-1, while with magnetic stirrer solution；
Step 2, manganese sulfate is added in the solution in step 1 and is dissolved；
Step 3, it will be dissolved in the solution in propylene glycol addition step 2；
Step 4, lithium acetate is dissolved into water, is then added in the solution in step 3, is reacted, formed in step 4
Solution need to meet following require: lithium: manganese: molar ratio=2:1.1:0.8 of phosphorus, the body of deionized water and propylene glycol in solution
Product ratio is 5:1.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
6.8, allow 1 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reaction kettle liter with helium, 5 min rear enclosed air inlet and air outlet of ventilation are passed through
Temperature reacts 8 h to after 200 DEG C；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, after the material that 1 step 7 obtains being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material that step 7 obtains in deionized water and alcohol
Concentration is 0.06g mL-1；
Step 9, by the material being collected at 60 DEG C, 24 h are dried in vacuo；
Step 10, sucrose is mixed, is uniformly mixed, the weight of the sucrose of incorporation is by step 9 treated material weight
10%；
Step 11, the material Jing Guo step 10 is carried out being cold-pressed into disk, disc-shaped material radius is 1 cm, with a thickness of 2
mm；
Step 12, the disk material after cold pressing is placed in tube furnace, the helium that purity is 99.99% is passed through, 850
1.5 h are calcined at DEG C.
After above-mentioned steps are handled, the lithium manganese phosphate material of the outer carbon coating and interior carbon dope that are prepared by sucrose has just been obtained
Material, capacity is 212 mA h g at 0.1 C-1。
Embodiment 3
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour cobalt lithium, the weight ratio of lithium, cobalt and P elements in the interior carbon dope lithium ion battery material are as follows: lithium: cobalt: phosphorus=1.6:1:1.
The embodiment the preparation method comprises the following steps: including the following steps:
Step 1, cobaltocene (transition metal source with carbon-based group) is mixed with deionized water, is passed through neon, ventilation speed
Rate is 180 cm3 min-1, while with magnetic stirrer solution；
Step 2, it adds phosphoric acid in the solution in step 1 and dissolves；
Step 3, the mixture of ethylene glycol and propylene glycol is added in the solution in step 2 and is dissolved；
Step 4, lithium bromide is dissolved into water, is then added in the solution in step 3, is reacted, lithium: cobalt: phosphorus
Molar ratio=4:1:1.5, the volume ratio of the mixture of solution Zhong Shui and two kinds of alcohol is 2:1.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
7.2, allow 1.2 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reaction kettle liter with argon gas, 20 min rear enclosed air inlet and air outlet of ventilation are passed through
Temperature reacts 3 h to after 220 DEG C；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, after the material that 2 steps 7 obtain being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material that step 7 obtains in deionized water and alcohol
Concentration is 0.02 g mL-1；
Step 9, by the material being collected at 100 DEG C, 10 h are dried in vacuo；
Step 10, lactose is mixed, is uniformly mixed, the weight for mixing lactose is by step 9 treated material weight
15%；
Step 11, the material Jing Guo step 10 being carried out being cold-pressed into disk, disc-shaped material radius is 2 cm, with a thickness of
1.5 mm；
Step 12, the disk material after cold pressing is placed in tube furnace, is passed through the Krypton that purity is 99.999%,
2 h are calcined at 750 DEG C.
After above-mentioned steps are handled, the cobalt phosphate lithium material of the outer carbon coating and interior carbon dope that are prepared by lactose has just been obtained
Material, capacity is 182 mA h g at 0.1C-1。
Embodiment 4
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour nickel lithium, the weight ratio of lithium, nickel and P elements in the interior carbon dope lithium ion battery material are as follows: lithium: nickel: phosphorus=1.5:1:1.1.
The interior carbon dope lithium ion battery material of the embodiment the preparation method comprises the following steps: including the following steps:
Step 1, by a phenyl-phosphonic acid (phosphorus source with carbon-based group) and dicyclopentadienyl nickel (transition metal source with carbon-based group)
Deionized water mixing, is passed through xenon, and Ventilation Rate is 200 cm3 min-1, while with magnetic stirrer solution；
Step 2, it by nickel chloride, is added to by being dissolved in the solution in step 1；
Step 3, it will be dissolved in the solution in ethylene glycol addition step 2；
Step 4, nickel chloride is dissolved into water, is then added in the solution in step 3, is reacted, shape in step 4
At solution need to meet following require: lithium: nickel: molar ratio=3:1.5:0.5 of phosphorus, the volume ratio of water and ethylene glycol in solution
Example is 4.5:1.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
8, allow 2 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reaction kettle liter with hydrogen, 15 min rear enclosed air inlet and air outlet of ventilation are passed through
Temperature reacts 6 h to after 240 DEG C；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, after the material that 2 steps 7 obtain being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material that step 7 obtains in deionized water and alcohol
Concentration is 0.02 g mL-1；
Step 9, by the material being collected at 90 DEG C, 24 h are dried in vacuo；
Step 10, maltose is mixed, is uniformly mixed, the weight for mixing maltose is by step 9 treated material weight
The 25% of amount；
Step 11, the material Jing Guo step 10 being carried out being cold-pressed into disk, disc-shaped material radius is 10 cm, with a thickness of
12 mm；
Step 12, the disk material after cold pressing is placed in tube furnace, is passed through hydrogen, 1 h is calcined at 900 DEG C.
After above-mentioned steps are handled, the LiNiPO material of the outer carbon coating and interior carbon dope that are prepared by maltose has just been obtained
Material, capacity is 192 mA h g at 0.1C-1。
Embodiment 5
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour iron lithium, the weight ratio of lithium, iron and P elements in the interior carbon dope lithium ion battery material are as follows: Li:Fe:P=1.2:1:1.2.
The interior carbon dope lithium ion battery material the preparation method comprises the following steps: including the following steps:
Step 1, by phytic acid (phosphorus source containing carbon-based group) and ferrocene (transition metal source containing carbon-based group) deionization
Water mixing, is passed through hydrogen, and Ventilation Rate is 250 cm3 min-1, while with magnetic stirrer solution；
Step 2, it adds phosphoric acid to by being dissolved in the solution in step 1；
Step 3, it will be dissolved in the solution in ethylene glycol addition step 2；
Step 4, lithium iodide is dissolved into water, is then added in the solution in step 3, is reacted, formed in step 4
Solution need to meet following require: lithium: iron: the volume ratio of water and ethyl alcohol is 3:1 in the molar ratio of phosphorus=3:1:1 solution.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
7.2, allow 1.2 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reaction kettle liter with hydrogen, 30 min rear enclosed air inlet and air outlet of ventilation are passed through
Temperature reacts 2 h to after 240 DEG C；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, after the material that 1 step 7 obtains being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material that step 7 obtains in deionized water and alcohol
Concentration is 0.15 g mL-1；
Step 9, by the material being collected at 98 DEG C, 20 h are dried in vacuo；
Step 10, phenolic resin is mixed, is uniformly mixed, the weight for mixing phenolic resin is by step 9 treated material
Expect the 25% of weight；
Step 11, the material Jing Guo step 10 being carried out being cold-pressed into disk, disc-shaped material radius is 8 cm, with a thickness of
1.5 mm；
Step 12, the disk material after cold pressing is placed in tube furnace, is passed through hydrogen, calcine 2h at 750 DEG C.
After above-mentioned steps are handled, the LiFePO4 of the outer carbon coating and interior carbon dope that are prepared by phenolic resin has just been obtained
Material, capacity is 218 mA h g at 0.1C-1。
Embodiment 6
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour manganese lithium, the weight ratio of lithium, manganese and P elements in the interior carbon dope lithium ion battery material are as follows: lithium: manganese: phosphorus=1.18:1:1.15.
The interior carbon dope lithium ion battery material the preparation method comprises the following steps: including the following steps:
Step 1, by phytic acid calcium (phosphorus source with carbon-based group), two luxuriant manganese (transition metal source with carbon-based group) with go from
Sub- water mixing, is passed through carbon monoxide, and Ventilation Rate is 220 cm3 min-1, while with magnetic stirrer solution；
Step 2, it will be dissolved in the solution in ethylene glycol addition step 1；
Step 3, lithium hydroxide and lithium acetate are dissolved into water, are then added in the solution in step 2, are reacted,
The solution formed in step 3 needs to meet following require: lithium: manganese: water and ethylene glycol in the molar ratio of phosphorus=4:0.5:1.2 solution
Volume ratio be 4:1.
Step 4, the pH value of measurement solution after step 3 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
10.5, allow 2 h of solution reaction；
Step 5, the solution after step 4 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reacts with carbon monoxide, 22 min rear enclosed air inlet and air outlet of ventilation are passed through
After kettle is warming up to 230 DEG C, 5 h are reacted；
Step 6, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 7, after the material that 2 steps 6 obtain being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee that the material that step 6 obtains is dense in deionized water and alcohol
Degree is 0.12 g mL-1；
Step 8, by the material being collected at 78 DEG C, 18 h are dried in vacuo；
Step 9, epoxy resin is mixed, is uniformly mixed, the weight for mixing epoxy resin is by step 8 treated material
Expect the 5% of weight；
Step 10, the material Jing Guo step 9 is carried out being cold-pressed into disk, disc-shaped material radius is 2 cm, with a thickness of 8
mm；
Step 11, the disk material after cold pressing is placed in tube furnace, is passed through high-purity CO, forged at 820 DEG C
Burn 2 h.
After above-mentioned steps are handled, the lithium manganese phosphate of the outer carbon coating and interior carbon dope that are prepared by epoxy resin has just been obtained
Material, capacity is 213 mA h g at 0.1C-1。
Embodiment 7
A kind of interior carbon dope lithium ion battery material, including the phosphate containing lithium and transition metal, it is characterised in that: described
Carbon dope in phosphate crystal containing lithium and transition metal, outer cladding carbon, the phosphate containing lithium and transition metal are phosphorus
Sour iron lithium, the weight ratio of lithium, iron and P elements in the interior carbon dope lithium ion battery material are as follows: Li:Fe:P=1.35:1:0.9.
The LiFePO 4 material the preparation method comprises the following steps: including the following steps:
Step 1, the mixture (phosphorus source with carbon-based group) of phytic acid calcium and phytic acid is mixed with deionized water, is passed through an oxygen
Change carbon, Ventilation Rate is 220 cm3 min-1, while with magnetic stirrer solution；
Step 2, it by ferrous sulfate and iron chloride, is added to by being dissolved in the solution in step 1；
Step 3, it will be dissolved in the solution in ethylene glycol addition step 2；
Step 4, lithium hydroxide and lithium acetate are dissolved into water, are then added in the solution in step 3, are reacted,
The solution formed in step 4 needs to meet following require: lithium: iron: molar ratio=2.5:0.8:0.5 of phosphorus, water and second two in solution
The volume ratio of alcohol is 4:1.
Step 5, the pH value of measurement solution after step 4 according to pH value lithium hydroxide or plants acid for adjusting pH value extremely
7.2, allow 2 h of solution reaction；
Step 6, the solution after step 5 is quickly transferred in stainless steel high temperature autoclave, and continues to use
Magnetic stirrer starts to warm up reaction, reacts with carbon monoxide, 22 min rear enclosed air inlet and air outlet of ventilation are passed through
After kettle is warming up to 230 DEG C, 5 h are reacted；
Step 7, it allows reaction kettle cooled to room temperature, tears the material that kettle is collected open；
Step 8, after the material that 2 steps 7 obtain being washed with deionized water, then alcohol is washed 1 time, and centrifugal treating is then carried out,
When washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee that the material that step 7 obtains is dense in deionized water and alcohol
Degree is 0.08 g mL-1；
Step 9, by the material being collected at 78 DEG C, 18 h are dried in vacuo；
Step 10, acetylene gas is mixed, is uniformly mixed, the weight for having acetylene gas of incorporation is by step 9 treated material
Expect the 5% of weight；
Step 11, the material Jing Guo step 10 is carried out being cold-pressed into disk, disc-shaped material radius is 2 cm, with a thickness of 8
mm；
Step 12, the disk material after cold pressing is placed in tube furnace, is passed through carbon monoxide and helium, at 820 DEG C
Calcine 2 h.
After above-mentioned steps are handled, the LiFePO4 material of the outer carbon coating and interior carbon dope that are prepared by acetylene gas has just been obtained
Material, capacity is 208 mA h g at 0.1C-1。
Abbreviation, English and Key Term define list: phytic acid (PhyA), phosphoric acid (PA), LiFePO4 (LFP), phytic acid
The LiFePO4 (IC/LFP) for the interior carbon doping that the interior carbon (IC) of preparation, the outer carbon (GC) of glucose preparation, phytic acid preparation are put, Portugal
The outer carbon coating of grape sugar preparation, outer carbon coating prepared by LiFePO4 (GC/LFP), the glucose of phosphoric acid preparation, phytic acid preparation
LiFePO4 (GC/IC/LFP), the lithium ion battery (LIBs), transmission electron microscope (TEM), high resolution TEM of interior carbon doping
(HRTEM), scanning electron microscope (SEM), the carbon packet that electrochemical stripping graphite oxide (ECGO), electrochemical stripping graphite oxide adulterate
Cover LFP(C/LFP/ECGO), x-ray photoelectron spectroscopy carbon 1s open score (XPS C1s)
Claims (7)
1. a kind of preparation method of interior carbon dope lithium ion battery material, it is characterised in that: include:
Step 1, by phosphorus source, water-soluble transition metal source, deionized water and water-soluble lithium source mixed dissolution shape with carbon-based group
At initial soln I；Or transition metal source, water-soluble phosphorus source, deionized water and water-soluble lithium source with carbon-based group are mixed
Dissolution forms initial soln II；Or by the mixture of the phosphorus source with carbon-based group and the transition metal source with carbon-based group, go
Ionized water and water-soluble lithium source mixed dissolution form initial soln III；Or by the phosphorus source with carbon-based group and with carbon-based group
The mixture of transition metal source, the water-soluble phosphorus source without carbon-based group or the water-soluble transition metal source without carbon-based group,
Deionized water and water-soluble lithium source mixed dissolution form initial soln IV；
Step 2, the pH value of initial soln I in regulating step 1, initial soln II, initial soln III and initial soln IV is to 5.5-
After 10.5,0.5-2 h is reacted；
Step 3, after the solution after step 2 being heated to 180-240 DEG C, 1-12 h is reacted；
Step 4, by after step 3 processing obtained material be washed with deionized water 0-2 times, then wash 1 time with ethyl alcohol, then into
Row centrifuge separation, when washing and alcohol are washed, the deionized water of addition and the amount of alcohol will guarantee material in deionized water and alcohol
Concentration is 0.01-0.15 g mL-1；
Step 5, dry by step 4 treated material；
Step 6, carbon source is mixed into the material after step 5 processing；
Step 7, by by step 6 treated material the mixed gas of inert gas, reducibility gas or both atmosphere
Under calcined, calcination temperature are as follows: 700-900 DEG C, calcination time are as follows: 1-6 h；
In step 1, lithium in the initial soln I, initial soln II, initial soln III and initial soln IV: transition metal: phosphorus
Molar ratio=(2-4): (0.5-1.5): (0.5-1.5).
2. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: step 1
Also to be added protective agent in middle initial soln I, initial soln II, initial soln III and initial soln IV, protective agent be ethylene glycol,
Glycerine or combination object.
3. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: step 2
In by the way that phytic acid or lithium hydroxide is added adjust the pH value of solution to 6.8-7.2,2 h of solution reaction.
4. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: step 3
In, after the solution after step 2 is quickly transferred in reaction kettle, 180-240 DEG C is heated to solution by reaction kettle
Afterwards, 1-12 h is reacted.
5. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: step 5
In, drying temperature is at 60 DEG C -120 DEG C, and drying time is 8-24 h, is dried using vacuum drying mode.
6. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: step 6
In, the amount of the carbon source of incorporation is the 5%-30% by step 5 treated material weight.
7. a kind of preparation method of interior carbon dope lithium ion battery material according to claim 1, it is characterised in that: in step
It is additionally provided with cold pressing step between 6 and step 7, disk is made in the material cold pressing that step 6 obtains, disc-shaped material radius is
0.5-10 cm, with a thickness of 0.5-12 mm, in step 7, calcination temperature is 750 DEG C, calcination time 2-3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710115761.5A CN106654239B (en) | 2017-03-01 | 2017-03-01 | A kind of interior carbon dope lithium ion battery material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710115761.5A CN106654239B (en) | 2017-03-01 | 2017-03-01 | A kind of interior carbon dope lithium ion battery material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106654239A CN106654239A (en) | 2017-05-10 |
| CN106654239B true CN106654239B (en) | 2019-09-24 |
Family
ID=58846995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710115761.5A Active CN106654239B (en) | 2017-03-01 | 2017-03-01 | A kind of interior carbon dope lithium ion battery material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106654239B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108400330B (en) * | 2018-03-08 | 2020-07-14 | 蒋央芳 | Preparation method of carbon-doped manganese (III) phosphate |
| CN111547734A (en) * | 2020-05-11 | 2020-08-18 | 蒋达金 | Preparation method of carbon-doped lithium iron borate |
| CN114613965A (en) * | 2022-03-22 | 2022-06-10 | 宜昌邦普循环科技有限公司 | Preparation method and application of lithium iron phosphate/carbon composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437338A (en) * | 2011-12-13 | 2012-05-02 | 中国科学院化学研究所 | Phosphate/carbon composite material, and preparation method and application thereof |
| CN104733729A (en) * | 2014-12-19 | 2015-06-24 | 营口航盛科技实业有限责任公司 | Industrialized reparation method of LiM1-xZxPO4/ C composite material |
| CN105375015A (en) * | 2015-12-18 | 2016-03-02 | 齐鲁工业大学 | Preparation method of carbon-coated mesoporous lithium titanium phosphate |
-
2017
- 2017-03-01 CN CN201710115761.5A patent/CN106654239B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437338A (en) * | 2011-12-13 | 2012-05-02 | 中国科学院化学研究所 | Phosphate/carbon composite material, and preparation method and application thereof |
| CN104733729A (en) * | 2014-12-19 | 2015-06-24 | 营口航盛科技实业有限责任公司 | Industrialized reparation method of LiM1-xZxPO4/ C composite material |
| CN105375015A (en) * | 2015-12-18 | 2016-03-02 | 齐鲁工业大学 | Preparation method of carbon-coated mesoporous lithium titanium phosphate |
Non-Patent Citations (1)
| Title |
|---|
| Self-Assembled LiFePO4/C Nano/Microspheres by Using Phytic Acid as Phosphorus Source;Jing Su等;《The Journal of Physical Chemistry C》;20120201;第116卷;5019-5024页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106654239A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101112979B (en) | Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium | |
| CN105789596B (en) | A kind of over capacity anode material for lithium-ion batteries and its preparation method and application | |
| CN104966831B (en) | A kind of lithium-rich manganese-based anode material, its preparation method and lithium ion battery | |
| CN104733708B (en) | A kind of preparation method of the nickle cobalt lithium manganate composite of Surface coating LiFePO4 | |
| CN106450273B (en) | Preparation method of power NCM523 material for improving high and low temperature performance | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| CN106654239B (en) | A kind of interior carbon dope lithium ion battery material and preparation method thereof | |
| CN109037649A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN109065871A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN108598467A (en) | The preparation method and alumina-coated nickel-cobalt lithium manganate cathode material and lithium ion battery of alumina-coated nickel-cobalt lithium manganate cathode material | |
| CN109755487A (en) | The nickle cobalt lithium manganate and preparation method thereof of the LiFePO4 cladding of metallic element doping | |
| CN113651303A (en) | Preparation method of nano flaky iron phosphate and LiFePO prepared by using same4Positive electrode active material/C | |
| CN106058240A (en) | Preparation method of high-voltage lithium battery composite with core-shell structure | |
| CN115321507A (en) | Method for preparing ferromanganese phosphate by coprecipitation and application thereof | |
| CN106935808A (en) | Positive electrode active materials and preparation method thereof and cell size and positive pole and lithium battery | |
| CN100483809C (en) | Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN108598411B (en) | Nitrogen-doped carbon-coated tin oxide/iron oxide composite material, preparation method thereof and lithium battery material | |
| CN106602046A (en) | Lithium ion battery silicate cathode material, and preparation and application thereof | |
| CN106946296B (en) | A kind of micron order monocrystalline lithium nickelate and its preparation method and application | |
| CN110563052B (en) | Preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material | |
| WO2024040905A1 (en) | Method for hydrothermal preparation of ferromanganese phosphate and use thereof | |
| CN110112371A (en) | A kind of method of surface coating modification Spinel positive electrode | |
| CN106207178A (en) | The preparation method of positive electrode, positive electrode and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |