CN109921098A - A kind of preparation method of aqueous super nano ferric phosphate lithium battery - Google Patents
A kind of preparation method of aqueous super nano ferric phosphate lithium battery Download PDFInfo
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- CN109921098A CN109921098A CN201811384155.4A CN201811384155A CN109921098A CN 109921098 A CN109921098 A CN 109921098A CN 201811384155 A CN201811384155 A CN 201811384155A CN 109921098 A CN109921098 A CN 109921098A
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Abstract
The present invention relates to lithium battery preparation field more particularly to a kind of preparation methods of aqueous super nano ferric phosphate lithium battery.Ferric phosphate lithium cell in the present invention is first by preparing positive and negative electrode slurry, obtained positive and negative electrode slurry is respectively coated in aluminium foil surface and obtains positive and negative electrode pole piece, electrolyte is then placed it in battery case and injected by carrying out lamination to positive and negative electrode pole piece, chemical conversion is finally completed and partial volume step obtains ferric phosphate lithium cell.The present invention overcomes ferric phosphate lithium cell in the prior art, performance is bad at low temperature, has good resistance to low temperature；Energy density is high；Security performance is more preferable, the smaller advantage of resistance.
Description
Technical field
The present invention relates to lithium battery preparation field more particularly to a kind of preparation sides of aqueous super nano ferric phosphate lithium battery
Method.
Background technique
It by lithium metal or lithium alloy is negative electrode material, using the battery of non-aqueous electrolytic solution that " lithium battery ", which is a kind of,.
Lithium metal battery is proposed and is studied by Gilbert N.Lewis earliest within 1912.When the 1970s,
M.S.Whittingham is proposed and the lithium ion battery that begins one's study.Since the chemical characteristic of lithium metal is very active, so that lithium is golden
Processing, preservation, the use of category, it is very high to environmental requirement.With the development of science and technology, present lithium battery has become master
Stream.
LiFePO4/graphite system is system relatively common in lithium ion secondary battery of new generation now, due to phosphoric acid
Not only reserves are very rich in the Nature for essential element iron, phosphorus in iron lithium, and relative low price, and green ring
It protects, superior performance, is of great significance for a wide range of popularize of pure electric automobile, hybrid vehicle；LiFePO4 power
Battery has stable olivine structural, so the battery made of this system is very safe, therefore largely in commercial vehicle
Using wherein mainly based on EV/HEV.Ferric phosphate lithium cell is demonstrated by fabulous high-temperature behavior, but in cryogenic property and has super
The field of high power requirements is not well positioned to meet customer requirement.
Such as a kind of a kind of preparation method of lithium battery disclosed in Chinese patent literature, Publication No.
CN104638247A comprising following steps: step 1: the preparation of active material；Step 2: the preparation of anode pole piece；Step 3:
The assembling of battery.Elemental sulfur insertion is made anode with nanometer level microporous porous carbon materials and meets material by the present invention, the material
Expect conductive good, large specific surface area, there is powerful adsorption capacity to the reduzate of sulphur, therefore can improve on the whole
Electric conductivity, utilization rate and the cyclicity of sulfur electrode are high with lithium/sulphur battery energy density prepared by it.But its lower temperature resistance
It can not promoted still, it can not be with good performance at a lower temperature.
Summary of the invention
The present invention is that performance is bad at low temperature for ferric phosphate lithium cell in the prior art in order to overcome, and providing one kind can
Meet a kind of aqueous super nano-grade lithium iron phosphate electricity in low temperature and under conditions of ultra high power requires with superperformance
The preparation method in pond.
For achieving the above object, the invention is realized by the following technical scheme:
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) anode sizing agent prepare: LiFePO 4 material is sanded, LiFePO4 powder particles are obtained, then by its with
Conductive agent and aqueous binders obtain anode sizing agent after carrying out mixing homogenate；
(1.2) prepared by negative electrode slurry: after artificial graphite, carboxymethyl cellulose, aqueous binders and conductive agent are mixed homogenate
Obtain negative electrode slurry；
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: applying carbon to aluminium foil surface, then coats anode sizing agent, warp to the aluminium foil surface for having applied carbon-coating
Anode pole piece is obtained after cutting baking；
(2.2) prepared by cathode pole piece: coating negative electrode slurry to aluminium foil surface, obtains cathode pole piece after cutting baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, and place it in battery case
In body and inject electrolyte；
(4) it is melted into: to the battery after being completed, certain electric current is given, so that battery positive and negative electrode pole piece is excited；
(5) partial volume: battery is subjected to charge and discharge to designated capabilities, partial volume is completed and obtains aqueous super nano ferric phosphate lithium battery.
Ferric phosphate lithium cell in the present invention distinguishes obtained positive and negative electrode slurry first by preparing positive and negative electrode slurry
Coated on aluminium foil surface and positive and negative electrode pole piece is obtained, then places it in battery case by carrying out lamination to positive and negative electrode pole piece
In and inject electrolyte, be finally completed chemical conversion and partial volume step obtain ferric phosphate lithium cell.LiFePO4 material in the present invention
The partial size of material and artificial graphite is smaller, has high energy density by the positive and negative electrode pole piece that it is prepared.Aluminium foil simultaneously
On precoated nano-C particles, therefore the adhesive fastness between positive electrode and carbon-coated aluminum foils is greatly improved, and produces
Battery has ultra-high magnifications, overlength circulation, outstanding low temperature, self-discharge performance and outstanding consistency.
Preferably, LiFePO4 powder particles D50≤4 μm after being sanded in the step (1), artificial stone
5 μm of D50 < of ink, the conductive agent are in acetylene black, Ketjen black, gas-phase growth of carbon fibre, carbon nanotube or graphene
One or more compositions, the aqueous binders be styrene-butadiene emulsion, ptfe emulsion, polyvinyl alcohol or poly- third
One of olefin(e) acid ester.
LiFePO4 powder particles D50 value in the prior art is usually less than equal to 10 μm, and the D50 value of artificial graphite is logical
Often less than it is equal to 20 μm, the D50 value of LiFePO4 powder particles and artificial graphite in the present invention is far smaller than the prior art
In size, therefore through the invention in the ferric phosphate lithium cell that is prepared of preparation method there is high energy density,
It still can effectively discharge electricity therein under cryogenic, to be provided with good cryogenic property.
Preferably, mass percent shared by each component in the step (1) in anode sizing agent is as follows: LiFePO4
Powder particles 90~94%, conductive agent 3~5% and aqueous binders 1%~7%.
Preferably, mass percent shared by each component in the step (1) in negative electrode slurry is as follows: artificial graphite
89%~95%, carboxymethyl cellulose 1%~3%, aqueous binders 1%~3% and conductive agent 0.5%~5%.
Preferably, in the step (1) artificial graphite the preparation method is as follows:
(S.1) preparation of polymer emulsion: in parts by weight to reaction kettle
Middle 20~35 parts of addition polystyrene, 20~35 parts of hydroxy-ethyl acrylate, 3~10 parts of vinyltriethoxysilane, then plus
Enter 40~50 parts of deionized water and 2~5 parts of polyoxyethylene sorbitol acid anhydride, potassium peroxydisulfate 0.3 is added thereto after mixing evenly
After~3 parts, emulsion polymerization 2~5 hours, polymer emulsion is obtained；
(S.2) be blended: take 50 parts of polymer emulsion, thereto be added 30~20 parts of novolac epoxy resin, after mixing evenly again to
30~40 parts of hard carbon are wherein added, is molded as the sphere of 0.5~3cm after mixing evenly, drying obtains presoma；
(S.3) it is graphitized: by the gradient increased temperature in an inert atmosphere of presoma obtained in step (2), obtaining artificial graphite.
It is with novolac epoxy resin and hard by first preparing polymer emulsion, then by it for artificial graphite in the present invention
Carbon mixing, is formed by high temperature graphitization.Polymer moiety therein can effectively become stone in graphitizing process
Ink, and its artificial graphite that cannot be transformed into graphite at high temperature, therefore be prepared by this method of hard carbon part its by being graphitized
Part and cannot graphited hard carbon part composition, the crystallinity of the carbon in hard carbon part is bad, and there are a large amount of defects, and
These defects can help to accommodate lithium ion；Two for certain specific structures, these hard carbon materials have biggish ratio
Surface area, the surface rich in mesoporous and micropore or relative coarseness, can occur the desorption of lithium ion in charge and discharge process
It is attached, it is also possible to lithium dimer and lithium ion cluster are formed in these holes；And not exclusively due to carbon material charing, material is also possible to
There are the remnants of H, N, O atom, and the atom adulterated can be bonded with Li, generate additional capacity.In addition, hard carbon structure is steady
Fixed and charge and discharge circulation life is long, and carbon lithium current potential can be higher than 0.2V, and security performance is more preferable, and in -20 DEG C of low temperature environment
Lower that cell resistance can be reduced to 20~30% with pure graphite-phase ratio, low temperature charges constant current than promoting 20~30%.
Preferably, the gradient increased temperature program is as follows: 300~500 DEG C keep the temperature 1~3 hour, then with 50 DEG C/min
Rate be warming up to 800~1200 DEG C keep the temperature 0.5~3 hour, be then warming up to 1600~2000 DEG C with the rate of 20 DEG C/min
Keep the temperature 30~60min.
Preferably, the aluminum foil thickness in the step (2) in anode pole piece is 10~20 μm, carbon layers having thicknesses are 2~6
μm, anode sizing agent density is 10~100mg/cm2, cathode pole piece with a thickness of 6~10 μm, negative electrode slurry surface density is 10~
50mg/cm2。
Preferably, positive and negative anodes pole piece is respectively 50/51 layer in the step (3).
Preferably, steps are as follows for chemical conversion in the step (4): being charged to the current versus cell of 0.02~0.05C
30~60 minutes；Battery vacuum-pumping is sealed later and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this
Process；Then battery is placed on 33~38 DEG C of agings 24~72 hours；Continue constant current with the current versus cell of 0.1~0.2C again to fill
Electricity, so that cell voltage is reached 3.65V chemical conversion step terminates.
Preferably, steps are as follows for partial volume in the step (5): by the battery current discharge of 0.5~1C to 2.0V,
Rest 5~10 minutes, then continue be charged and discharged to capacity 40% or so with 0.5~1C electric current, battery completes partial volume.
Therefore, the invention has the following advantages:
(1) there is good resistance to low temperature；
(2) energy density is high；
(3) security performance is more preferable, and resistance is smaller.
Specific embodiment
Technical solution of the present invention is made to further describe explanation below by specific embodiment.
If saying that the raw material of use is raw material commonly used in the art without specified otherwise, in the embodiment of the present invention, implement
Method employed in example, is the conventional method of this field.
Embodiment 1
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) prepared by anode sizing agent: LiFePO 4 material is sanded, the LiFePO4 powder particles of D50≤4 μm are obtained,
Then by it according to such as formula: LiFePO4 powder particles 90%, acetylene black 5% and styrene-butadiene emulsion 5% carries out mixing homogenate
After obtain anode sizing agent；
(1.2) negative electrode slurry prepare: according to formula: artificial graphite 89%%, carboxymethyl cellulose 3%, styrene-butadiene emulsion 3% and
Negative electrode slurry is obtained after the mixing homogenate of acetylene black 5%.
Wherein the artificial graphite the preparation method is as follows:
(S.1) 20 parts of polystyrene, acrylic acid hydroxyl second the preparation of polymer emulsion: is added into reaction kettle in parts by weight
Then 40 parts of deionized water and 2 parts of polyoxyethylene sorbitol acid anhydride, stirring is added in 20 parts of ester, 3 parts of vinyltriethoxysilane
After 0.3 part of potassium peroxydisulfate, emulsion polymerization 2 hours is added thereto after uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 30 parts of novolac epoxy resin are added thereto, after mixing evenly again thereto
30 parts of hard carbon are added, is molded as the sphere of 0.5cm after mixing evenly, drying obtains presoma；
(S.3) be graphitized: by presoma obtained in step (2), gradient increased temperature, temperature program are as follows in an inert atmosphere:
300 DEG C keep the temperature 1 hour, are then warming up to 800 DEG C with the rate of 50 DEG C/min and keep the temperature 0.5 hour, then with the speed of 20 DEG C/min
Rate is warming up to 1600 DEG C of heat preservation 30min, obtains artificial graphite.
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: the carbon of 2 μ m-thicks is applied to the aluminium foil surface with a thickness of 10 μm, then to the aluminium foil for having applied carbon-coating
It is 10mg/cm that surface, which coats density,2Anode sizing agent, through cutting baking after obtain anode pole piece；
(2.2) prepared by cathode pole piece: being 10mg/cm to the aluminium foil surface of 6 μ m-thicks coating surface density2Negative electrode slurry, through cutting
Cathode pole piece is obtained after baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, positive and negative anodes pole piece is respectively
50/51 layer, and place it in battery case and inject electrolyte.
(4) it is melted into: to the battery after being completed, being charged to 30 minutes with the current versus cell of 0.02C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 33
DEG C aging 24 hours；Continue constant-current charge with the current versus cell of 0.1C again, cell voltage is made to reach 3.65V chemical conversion step knot
Beam.
(5) partial volume: the battery current discharge of 0.5C to 2.0V is rested 5 minutes, then with 0.5C electric current continue charging and
40% or so of capacity is discharged into, battery completes partial volume and obtains aqueous super nano ferric phosphate lithium battery.
Embodiment 2
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) prepared by anode sizing agent: LiFePO 4 material is sanded, the LiFePO4 powder particles of D50≤4 μm are obtained,
Then by it according to such as formula: LiFePO4 powder particles 94%, Ketjen black 5% and ptfe emulsion 1% mix
Anode sizing agent is obtained after closing homogenate；
(1.2) prepared by negative electrode slurry: according to formula: artificial graphite 95%, carboxymethyl cellulose 1%, ptfe emulsion 1%
And negative electrode slurry is obtained after the mixing homogenate of Ketjen black 3%.
Wherein the artificial graphite the preparation method is as follows:
(S.1) 20 parts of polystyrene, acrylic acid hydroxyl second the preparation of polymer emulsion: is added into reaction kettle in parts by weight
Then 35 parts of ester, 10 parts of vinyltriethoxysilane are added 50 parts of deionized water and 5 parts of polyoxyethylene sorbitol acid anhydride, stir
After 3 parts of potassium peroxydisulfate, emulsion polymerization 5 hours are added thereto after mixing uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 20 parts of novolac epoxy resin are added thereto, after mixing evenly again thereto
40 parts of hard carbon are added, is molded as the sphere of 3cm after mixing evenly, drying obtains presoma；
(S.3) be graphitized: by presoma obtained in step (2), gradient increased temperature, temperature program are as follows in an inert atmosphere:
500 DEG C keep the temperature 3 hours, are then warming up to 1200 DEG C with the rate of 50 DEG C/min and keep the temperature 3 hours, then with the rate of 20 DEG C/min
2000 DEG C of heat preservation 60min are warming up to, artificial graphite is obtained.
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: the carbon of 6 μ m-thicks is applied to the aluminium foil surface with a thickness of 20 μm, then to the aluminium foil for having applied carbon-coating
It is 100mg/cm that surface, which coats density,2Anode sizing agent, through cutting baking after obtain anode pole piece；
(2.2) prepared by cathode pole piece: being 50mg/cm to the aluminium foil surface of 10 μ m-thicks coating surface density2Negative electrode slurry, through cutting
Cathode pole piece is obtained after baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, positive and negative anodes pole piece is respectively
50/51 layer, and place it in battery case and inject electrolyte.
(4) it is melted into: to the battery after being completed, being charged to 60 minutes with the current versus cell of 0.05C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 38
DEG C aging 72 hours；Continue constant-current charge with the current versus cell of 0.2C again, cell voltage is made to reach 3.65V chemical conversion step knot
Beam.
(5) partial volume: the battery current discharge of 1C is rested 10 minutes to 2.0V, then is continued to charge and be put with 1C electric current
Electricity arrives 40% or so of capacity, and battery completes partial volume and obtains aqueous super nano ferric phosphate lithium battery.
Embodiment 3
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) prepared by anode sizing agent: LiFePO 4 material is sanded, the LiFePO4 powder particles of D50≤4 μm are obtained,
Then by it according to such as formula: LiFePO4 powder particles 92%, gas-phase growth of carbon fibre 4% and polyvinyl alcohol 4% carry out
Anode sizing agent is obtained after mixing homogenate；
(1.2) prepared by negative electrode slurry: according to formula: artificial graphite 92%, carboxymethyl cellulose 2%, polyvinyl alcohol 2% and gas
Negative electrode slurry is obtained after the mixing homogenate of phase grown carbon fiber 4%.
Wherein the artificial graphite the preparation method is as follows:
(S.1) 25 parts of polystyrene, acrylic acid hydroxyl second the preparation of polymer emulsion: is added into reaction kettle in parts by weight
Then 48 parts of deionized water and 2 parts of polyoxyethylene sorbitol acid anhydride, stirring is added in 25 parts of ester, 8 parts of vinyltriethoxysilane
After 1.5 parts of potassium peroxydisulfate, emulsion polymerization 3 hours are added thereto after uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 25 parts of novolac epoxy resin are added thereto, after mixing evenly again thereto
35 parts of hard carbon are added, is molded as the sphere of 2cm after mixing evenly, drying obtains presoma；
(S.3) be graphitized: by presoma obtained in step (2), gradient increased temperature, temperature program are as follows in an inert atmosphere:
400 DEG C keep the temperature 2 hours, are then warming up to 1000 DEG C with the rate of 50 DEG C/min and keep the temperature 2 hours, then with the rate of 20 DEG C/min
1800 DEG C of heat preservation 45min are warming up to, artificial graphite is obtained.
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: the carbon of 4 μ m-thicks is applied to the aluminium foil surface with a thickness of 18 μm, then to the aluminium foil for having applied carbon-coating
It is 60mg/cm that surface, which coats density,2Anode sizing agent, through cutting baking after obtain anode pole piece；
(2.2) prepared by cathode pole piece: being 30mg/cm to the aluminium foil surface of 8 μ m-thicks coating surface density2Negative electrode slurry, through cutting
Cathode pole piece is obtained after baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, positive and negative anodes pole piece is respectively
50/51 layer, and place it in battery case and inject electrolyte.
(4) it is melted into: to the battery after being completed, being charged to 40 minutes with the current versus cell of 0.03C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 35
DEG C aging 48 hours；Continue constant-current charge with the current versus cell of 0.2C again, cell voltage is made to reach 3.65V chemical conversion step knot
Beam.
(5) partial volume: the battery current discharge of 0.8C to 2.0V is rested 8 minutes, then with 0.6C electric current continue charging and
40% or so of capacity is discharged into, battery completes partial volume and obtains aqueous super nano ferric phosphate lithium battery.
Embodiment 4
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) prepared by anode sizing agent: LiFePO 4 material is sanded, the LiFePO4 powder particles of D50≤4 μm are obtained,
Then by it according to such as formula: LiFePO4 powder particles 93%, carbon nanotube or graphene 5% and polyacrylate
2% carry out mixing homogenate after obtain anode sizing agent；
(1.2) negative electrode slurry prepare: according to formula: artificial graphite 94%, carboxymethyl cellulose 3%, polyacrylate 2% and
Negative electrode slurry is obtained after the mixing homogenate of carbon nanotube 1%.
Wherein the artificial graphite the preparation method is as follows:
(S.1) 30 parts of polystyrene, acrylic acid hydroxyl second the preparation of polymer emulsion: is added into reaction kettle in parts by weight
Then 25 parts of ester, 8 parts of vinyltriethoxysilane are added 48 parts of deionized water and 2.5 parts of polyoxyethylene sorbitol acid anhydride, stir
After 1.5 parts of potassium peroxydisulfate, emulsion polymerization 4 hours are added thereto after mixing uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 26 parts of novolac epoxy resin are added thereto, after mixing evenly again thereto
34 parts of hard carbon are added, is molded as the sphere of 2cm after mixing evenly, drying obtains presoma；
(S.3) be graphitized: by presoma obtained in step (2), gradient increased temperature, temperature program are as follows in an inert atmosphere:
450 DEG C keep the temperature 2.5 hours, are then warming up to 1100 DEG C with the rate of 50 DEG C/min and keep the temperature 0.5 hour, then with 20 DEG C/min's
Rate is warming up to 1850 DEG C of heat preservation 50min, obtains artificial graphite.
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: the carbon of 3 μ m-thicks is applied to the aluminium foil surface with a thickness of 18 μm, then to the aluminium foil for having applied carbon-coating
It is 80mg/cm that surface, which coats density,2Anode sizing agent, through cutting baking after obtain anode pole piece；
(2.2) prepared by cathode pole piece: being 25mg/cm to the aluminium foil surface of 9 μ m-thicks coating surface density2Negative electrode slurry, through cutting
Cathode pole piece is obtained after baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, positive and negative anodes pole piece is respectively
50/51 layer, and place it in battery case and inject electrolyte.
(4) it is melted into: to the battery after being completed, being charged to 40 minutes with the current versus cell of 0.03C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 35
DEG C aging 36 hours；Continue constant-current charge with the current versus cell of 0.2C again, cell voltage is made to reach 3.65V chemical conversion step knot
Beam.
(5) partial volume: the battery current discharge of 1C is rested 5 minutes to 2.0V, then is continued to charge and be put with 0.8C electric current
Electricity arrives 40% or so of capacity, and battery completes partial volume and obtains aqueous super nano ferric phosphate lithium battery.
Embodiment 5
A kind of preparation method of aqueous super nano ferric phosphate lithium battery, the preparation method the following steps are included:
(1) prepared by positive and negative electrode slurry:
(1.1) prepared by anode sizing agent: LiFePO 4 material is sanded, the LiFePO4 powder particles of D50≤4 μm are obtained,
Then by it according to such as formula: LiFePO4 powder particles 94%, graphene 4% and styrene-butadiene emulsion 2% carries out mixing homogenate
After obtain anode sizing agent；
(1.2) prepared by negative electrode slurry: according to formula: artificial graphite 91%, carboxymethyl cellulose 2%, polyvinyl alcohol 2% and stone
Negative electrode slurry is obtained after the black mixing of alkene 5% homogenate.
Wherein the artificial graphite the preparation method is as follows:
(S.1) 26 parts of polystyrene, acrylic acid hydroxyl second the preparation of polymer emulsion: is added into reaction kettle in parts by weight
Then 48 parts of deionized water and 3 parts of polyoxyethylene sorbitol acid anhydride, stirring is added in 30 parts of ester, 4 parts of vinyltriethoxysilane
After 0.5 part of potassium peroxydisulfate, emulsion polymerization 2.5 hours is added thereto after uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 25 parts of novolac epoxy resin are added thereto, after mixing evenly again thereto
36 parts of hard carbon are added, is molded as the sphere of 2.5cm after mixing evenly, drying obtains presoma；
(S.3) be graphitized: by presoma obtained in step (2), gradient increased temperature, temperature program are as follows in an inert atmosphere:
4500 DEG C keep the temperature 3 hours, are then warming up to 1200 DEG C with the rate of 50 DEG C/min and keep the temperature 3 hours, then with the speed of 20 DEG C/min
Rate is warming up to 1600 DEG C of heat preservation 60min, obtains artificial graphite.
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: the carbon of 6 μ m-thicks is applied to the aluminium foil surface with a thickness of 20 μm, then to the aluminium foil for having applied carbon-coating
It is 75mg/cm that surface, which coats density,2Anode sizing agent, through cutting baking after obtain anode pole piece；
(2.2) prepared by cathode pole piece: being 50mg/cm to the aluminium foil surface of 6 μ m-thicks coating surface density2Negative electrode slurry, through cutting
Cathode pole piece is obtained after baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, positive and negative anodes pole piece is respectively
50/51 layer, and place it in battery case and inject electrolyte.
(4) it is melted into: to the battery after being completed, being charged to 45 minutes with the current versus cell of 0.05C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 38
DEG C aging 48 hours；Continue constant-current charge with the current versus cell of 0.2C again, cell voltage is made to reach 3.65V chemical conversion step knot
Beam.
(5) partial volume: the battery current discharge of 0.5C is rested 5 minutes to 2.0V, then is continued to charge and be put with 1C electric current
Electricity arrives 40% or so of capacity, and battery completes partial volume and obtains aqueous super nano ferric phosphate lithium battery.
The aqueous super nano ferric phosphate lithium battery and existing commercially available ferric phosphate lithium cell that Examples 1 to 5 is obtained
It compares, it is tested respectively under room temperature and cryogenic conditions.Its test result is as shown in table 1.
Table 1
It is shown by the above results, it is identical in capacity for aqueous super nano ferric phosphate lithium battery obtained through the invention
In the case where, there is higher low temperature charging constant current ratio compared to commercially available ferric phosphate lithium cell under cryogenic, show
Its performance under cryogenic.
Claims (10)
1. a kind of preparation method of aqueous super nano ferric phosphate lithium battery, which is characterized in that the preparation method include with
Lower step:
(1) prepared by positive and negative electrode slurry:
(1.1) anode sizing agent prepare: LiFePO 4 material is sanded, LiFePO4 powder particles are obtained, then by its with
Conductive agent and aqueous binders obtain anode sizing agent after carrying out mixing homogenate；
(1.2) prepared by negative electrode slurry: after artificial graphite, carboxymethyl cellulose, aqueous binders and conductive agent are mixed homogenate
Obtain negative electrode slurry；
(2) prepared by positive and negative electrode pole piece:
(2.1) prepared by anode pole piece: applying carbon to aluminium foil surface, then coats anode sizing agent, warp to the aluminium foil surface for having applied carbon-coating
Anode pole piece is obtained after cutting baking；
(2.2) prepared by cathode pole piece: coating negative electrode slurry to aluminium foil surface, obtains cathode pole piece after cutting baking；
(3) lamination fluid injection: anode pole piece and cathode pole piece are replaced into lamination according to Z-shaped mode, and place it in battery case
In body and inject electrolyte；
(4) it is melted into: to the battery after being completed, certain electric current is given, so that battery positive and negative electrode pole piece is excited；
(5) partial volume: battery is subjected to charge and discharge to designated capabilities, partial volume is completed and obtains aqueous super nano ferric phosphate lithium battery.
2. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1, which is characterized in that institute
LiFePO4 powder particles D50≤4 μm after being sanded in the step of stating (1), 5 μm of the D50 < of artificial graphite are described
Conductive agent is one of acetylene black, Ketjen black, gas-phase growth of carbon fibre, carbon nanotube or graphene or numerous compositions,
The aqueous binders are one of styrene-butadiene emulsion, ptfe emulsion, polyvinyl alcohol or polyacrylate.
3. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1 or 2, feature exist
In mass percent shared by each component in the step (1) in anode sizing agent is as follows: LiFePO4 powder particles 90 ~
94%, conductive agent 3 ~ 5% and aqueous binders 1% ~ 7%.
4. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1 or 2, feature exist
In mass percent shared by each component in the step (1) in negative electrode slurry is as follows: artificial graphite 89% ~ 95%, carboxymethyl
Cellulose 1% ~ 3%, aqueous binders 1% ~ 3% and conductive agent 0.5% ~ 5%.
5. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1 or 2, feature exist
In, in the step (1) artificial graphite the preparation method is as follows:
(S.1) preparation of polymer emulsion: into reaction kettle be added 20 ~ 35 parts of polystyrene, 20 ~ 35 parts of hydroxy-ethyl acrylate,
3 ~ 10 parts of vinyltriethoxysilane, 40 ~ 50 parts of deionized water and 2 ~ 5 parts of polyoxyethylene sorbitol acid anhydride are then added, stir
After 0.3 ~ 3 part of potassium peroxydisulfate, emulsion polymerization 2 ~ 5 hours is added thereto after mixing uniformly, polymer emulsion is obtained；
(S.2) it is blended: taking 50 parts of polymer emulsion, 30 ~ 20 parts of novolac epoxy resin are added thereto, after mixing evenly again to it
Middle 30 ~ 40 parts of addition hard carbon, it is molded as the sphere of 0.5 ~ 3cm of diameter after mixing evenly, drying obtains presoma；
(S.3) it is graphitized: by presoma obtained in step (2) gradient increased temperature in an inert atmosphere, obtaining artificial graphite.
6. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 5, which is characterized in that institute
The gradient increased temperature program stated is as follows: 300 ~ 500 DEG C keep the temperature 1 ~ 3 hour, are then warming up to 800 ~ 1200 with the rate of 50 DEG C/min
DEG C heat preservation 0.5 ~ 3 hour, 1600 ~ 2000 DEG C of 30 ~ 60min of heat preservation are then warming up to the rate of 20 DEG C/min.
7. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1, which is characterized in that institute
Aluminum foil thickness in the step of stating (2) in anode pole piece is 10 ~ 20 μm, and carbon layers having thicknesses are 2 ~ 6 μm, anode sizing agent density is 10 ~
100mg/cm2, for cathode pole piece with a thickness of 6 ~ 10 μm, negative electrode slurry surface density is 10 ~ 50 mg/cm2。
8. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1, which is characterized in that institute
Positive and negative anodes pole piece is respectively 50/51 layer in the step of stating (3).
9. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1, which is characterized in that institute
Steps are as follows for chemical conversion in the step of stating (4): being charged to 30 ~ 60 minutes with the current versus cell of 0.02 ~ 0.05C；Later by battery
It vacuumizes heat-sealing and carries out Degas pumping encapsulation, test inside battery does not have bubble to complete this process；Then battery is placed on 33
~ 38 DEG C aging 24 ~ 72 hours；Continue constant-current charge with the current versus cell of 0.1 ~ 0.2C again, cell voltage is made to reach 3.65Vization
Terminate at step.
10. a kind of preparation method of aqueous super nano ferric phosphate lithium battery according to claim 1, which is characterized in that
Steps are as follows for partial volume in the step (5): the battery current discharge of 0.5 ~ 1C being rested 5 ~ 10 minutes to 2.0V, then is used
0.5 ~ 1C electric current continues to be charged and discharged to 40% of capacity or so, and battery completes partial volume.
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Effective date of registration: 20211110 Address after: 311215 No. 855, Jianshe Second Road, economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: Wanxiang 123 Co., Ltd Address before: 311215 No. 855, Jianshe Second Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: Wanxiang 123 Co., Ltd Patentee before: Wanxiang Group Co., Ltd |