阅读说明：本技术 一种高安全性一次锂锰电池及其制备方法 (High-safety disposable lithium-manganese battery and preparation method thereof ) 是由 黄碧英 黄耀泽 唐天文 于 2020-12-08 设计创作，主要内容包括：本发明公开了一种高安全性一次锂锰电池及其制备方法,一次锂锰电池包括正极片、负极片、陶瓷隔膜、电解液以及电池壳,正极片、陶瓷隔膜、负极片、陶瓷隔膜依次重复层叠后形成为干电芯,一次锂锰电池由干电芯放入电池壳并经过注入电解液、老化、封口、老化制成,其创新点在于：负极片经过电化学预掺锂,将“满荷电态的二次锂电池负极片”或“零荷电态的锂/碳半电池正极片”转变成预锂化负极片,正极片的正反两面均设有正极片预留极耳,负极片的正反两面均设有负极片预留极耳,本发明的一次锂锰电池在经过撞击、挤压、针刺测试后,无起火、爆燃、爆炸的现象,安全性能高于传统的一次锂锰电池。(The invention discloses a high-safety disposable lithium-manganese battery and a preparation method thereof, the disposable lithium-manganese battery comprises a positive plate, a negative plate, a ceramic diaphragm, electrolyte and a battery shell, the positive plate, the ceramic diaphragm, the negative plate and the ceramic diaphragm are sequentially and repeatedly laminated to form a dry battery core, the disposable lithium-manganese battery is prepared by putting the dry battery core into the battery shell and injecting the electrolyte, aging, sealing and aging, and the disposable lithium-manganese battery is characterized in that: the negative plate is electrochemically pre-doped with lithium, the secondary lithium battery negative plate in a full charge state or the lithium/carbon half-battery positive plate in a zero charge state is converted into a pre-lithiation negative plate, the positive plate reserved lugs are arranged on the positive surface and the negative surface of the positive plate, and the negative plate reserved lugs are arranged on the positive surface and the negative surface of the negative plate.)

1. The utility model provides a high security's lithium manganese cell once, lithium manganese cell once includes positive plate (1), negative pole piece, ceramic diaphragm (3), electrolyte and battery case (4), and positive plate (1), ceramic diaphragm (3), lithiation negative pole piece in advance, ceramic diaphragm (3) repeat the lamination in proper order and form into dry electric core, lithium manganese cell once by dry electric core is put into battery case (4) and through pouring into electrolyte, ageing, seal, ageing the preparation, its characterized in that: the negative plate is electrochemically pre-doped with lithium, so that a secondary lithium battery negative plate in a full charge state or a lithium/carbon half-battery positive plate in a zero charge state is converted into a pre-lithiation negative plate (2), positive plate reserved lugs (11) are arranged on the front surface and the back surface of the positive plate (1), and negative plate reserved lugs (21) are arranged on the front surface and the back surface of the pre-lithiation negative plate (2);

the dry cell comprises a positive electrode full tab and a negative electrode full tab, when a plurality of positive electrode sheets (1) are stacked, the reserved tabs (11) of the positive electrode sheets are mutually aligned and form multiple positive electrode sheet tabs, the multiple positive electrode sheet tabs and the planar metal sheet current collectors are welded to form the positive electrode full tab, when a plurality of pre-lithiation negative electrode sheets (2) are stacked, the reserved tabs (21) of the negative electrode sheets are mutually aligned and form multiple negative electrode sheet tabs, and the multiple negative electrode sheet tabs and the planar metal sheet current collectors are welded to form the negative electrode full tab;

the ceramic diaphragm (3) is a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability;

the electrolyte is prepared by mixing 0.7-2 mol of lithium salt and an organic solvent with high boiling point and low vapor pressure, wherein the organic solvent is carbonic ester or carboxylic ester;

the both ends of battery case (4) are equipped with the anodal mass flow body of casing (41), the body negative pole mass flow body (42) respectively, once lithium manganese battery by dry electric core is put into battery case (4), and makes anodal full utmost point ear the full utmost point ear of negative pole is connected respectively the anodal mass flow body of casing (41) the body negative pole mass flow body (42), and through pouring into electrolyte, ageing, seal, ageing the making.

2. The high-safety primary lithium manganese battery according to claim 1, wherein: the lithium salt is lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide, lithium trifluoro (methylsulfonyl) sulfonate and lithium iodide;

the high boiling point and low vapor pressure carbonate is ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate;

the carboxylic ester with high boiling point and low vapor pressure is butyl acetate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone and delta-valerolactone.

3. The high-safety primary lithium manganese battery according to claim 1, wherein: the battery shell (4) is square, and the material of the battery shell (4) is steel, aluminum or aluminum plastic.

4. A method for preparing a high-safety disposable lithium manganese battery according to any one of claims 1 to 3, characterized in that: the method specifically comprises the following steps:

s1, preparing the positive plate

Preparing anode slurry from 85-98% of anode material, 1-10% of conductive agent and 1-15% of binder by mass percent, and uniformly coating the anode slurry on a current collector aluminum mesh (101)The positive electrode slurry forms positive electrode coatings (14) on the positive and negative surfaces of the current collector aluminum mesh (101), positive blank areas are reserved on four edges of the positive coating (14) and four edges of the current collector aluminum mesh (101), the positive blank area is divided into a positive plate reserved lug (11) and 3 positive diaphragm wrapping areas (12), the positive plate reserved tab (11) and one of the positive diaphragm wrapping areas (12) are positioned at two ends of the positive coating (14), the other two anode diaphragm wrapping areas (12) are positioned at two sides of the anode coating (14), the current collector aluminum net (101) coated with the anode coating (14) is placed in a vacuum drying box, after being baked at 85 ℃ in a vacuum environment with-0.09 to-0.1 MPa, rolling the mixture to a compact state by using a rolling device, wherein the surface density of the positive electrode coating (14) is 50-100 mg/cm.²Then baking the whole body at 110 ℃ in a vacuum environment of-0.09 to-0.1 MPa to obtain a positive plate;

s2 preparation of pre-lithiated negative plate (2)

A. Preparing a spare pole piece: make the negative pole material of mass percent 85% -98%, 1% -10% conductive agent, 1% -15% binder make negative pole thick liquids and evenly coat the positive and negative two sides of mass flow body copper net (102), the negative pole thick liquids are in the positive and negative two sides of mass flow body copper net (102) form negative pole coating (24), four limits of negative pole coating (24) respectively with four edges of mass flow body copper net (102) all reserve and have negative pole blank space, negative pole blank space is divided into utmost point ear (21) and 3 negative pole diaphragm parcel district (22) are reserved to the negative pole piece, utmost point ear (21) and one of them negative pole diaphragm parcel district (22) are reserved to the negative pole piece are located the both ends of negative pole coating (24), other two negative pole diaphragm parcel district (22) are located the both sides of negative pole coating (24), the mass flow body copper net (102) that will scribble negative pole coating (24) is put in the vacuum drying oven, baking the anode coating at 85 ℃ in a vacuum environment of-0.09 to-0.1 MPa, and rolling the anode coating to a compact state by using a calender so that the surface density of the anode coating (24) is 25 to 50mg/cm²Then the whole is in a vacuum environment of-0.09 to-0.1 MPaBaking at 110 ℃ to obtain a spare pole piece;

B. preparing a secondary lithium battery: b, preparing the spare pole piece obtained in the step A into a secondary lithium battery according to a conventional preparation process, wherein the spare pole piece becomes a negative pole piece of the secondary lithium battery;

C. preparation of lithium/carbon half-cells: b, preparing the spare pole piece obtained in the step A into a lithium/carbon half-cell according to a conventional preparation process, wherein the spare pole piece becomes a lithium/carbon half-cell positive plate;

D. preparing a prelithiation negative plate (2):

charging the secondary lithium battery in the step B, disassembling the secondary lithium battery in an inert gas atmosphere environment, and separating out the negative plate of the secondary lithium battery to obtain a pre-lithiated negative plate (2);

and II, discharging the lithium/carbon half cell in the step C, disassembling the lithium/carbon half cell in an inert gas atmosphere, and separating out the positive plate of the lithium/carbon half cell to obtain the pre-lithiation negative plate (2).

S3 preparation of nano microporous ceramic diaphragm

Coating the front side and the back side of the ceramic diaphragm (3) with a nano alumina coating, and removing a solvent in the alumina coating by means of a vacuum baking oven to obtain a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability, wherein the area of the nano microporous ceramic diaphragm is larger than that of a manganese dioxide positive plate or a pre-lithiation negative plate;

s4, preparing dry electric core

The manganese dioxide positive plate, the nano microporous ceramic diaphragm, the pre-lithiation negative plate and the nano microporous ceramic diaphragm are combined and laminated to form a dry battery cell; in the lamination process, 3 positive electrode membrane wrapping areas (12) are respectively wrapped by membranes (103), and the reserved tabs (11) of the positive electrode plates are laminated and gathered together to form the multiple positive electrode tabs; 3 negative electrode diaphragm wrapping areas (22) are respectively wrapped by diaphragms (103), and the reserved tabs (21) of the negative electrode sheets are stacked and gathered together to form the multiple negative electrode tabs; the multiple positive electrode tabs and the planar metal sheet current collector are welded to form positive electrode full tabs, and the multiple negative electrode tabs and the planar metal sheet current collector are welded to form negative electrode full tabs;

s5, assembling battery

And putting the dry battery cell into a battery case (4) at a certain temperature and after applying a certain pressure, respectively connecting a positive current collector (41) and a negative current collector (42) of the case with a positive full lug and a negative full lug, and injecting the electrolyte into the case for aging, sealing and aging to obtain the primary lithium manganese battery.

5. The method for preparing a high-safety disposable lithium manganese battery according to claim 4, wherein: the anode material is manganese dioxide.

6. The method for preparing a high-safety disposable lithium manganese battery according to claim 4, wherein: the negative electrode material is one or the combination of more than two of mesocarbon microbeads, artificial graphite and silicon-carbon composite material.

7. The method for preparing a high-safety disposable lithium manganese battery according to claim 4, wherein: the current collector aluminum mesh (101) is an aluminum mesh with high porosity and is 10-25 um thick; the current collector copper mesh (102) is a copper mesh with high porosity and is 6-20 um thick.

8. The method for preparing a high-safety disposable lithium manganese battery according to claim 4, wherein: the conductive agent is one or the combination of more than two of superconductive carbon black, conductive graphite, carbon fiber, carbon nano tube and graphene; the binder is one or the combination of more than two of polyvinylidene fluoride, styrene butadiene rubber and sodium carboxymethyl cellulose.

Technical Field

The invention relates to the technical field of lithium batteries, in particular to a high-safety disposable lithium-manganese battery and a preparation method thereof.

Background

The lithium manganese battery has the advantages of high voltage platform, large energy density, small self-discharge rate, long storage time and the like, so that the lithium manganese battery has wider and wider application range in the market. However, the traditional lithium manganese battery has certain potential safety hazard in the use process, which mainly comprises the following steps: when the lithium manganese battery is impacted by a heavy object, extruded, needled and the like, safety accidents such as fire, deflagration, explosion and the like are easily caused.

The main factors influencing the safety performance of the lithium manganese battery are as follows: the traditional lithium-manganese battery adopts a metal lithium belt as a negative plate, because the metal lithium is very active, when the battery is subjected to the action of external force and the metal lithium and electrolyte in the battery are exposed to the air, the metal lithium is very easy to react with oxygen, nitrogen and moisture in the air, particularly react with water to generate hydrogen, and an organic solvent in the electrolyte also simultaneously carries out a series of decomposition reactions, so that the ignition, deflagration and explosion of the battery are very easy to cause; secondly, the traditional lithium manganese battery adopts a polypropylene common diaphragm with low melting point, when metal lithium, electrolyte and oxygen, nitrogen and moisture in the air react to generate a large amount of heat energy, or the internal temperature rise of the battery in the working process is overhigh, the common diaphragm is easy to shrink and break holes so that a positive plate and a negative plate are directly contacted to cause short circuit, and the ignition, deflagration and explosion of the battery are rapidly caused; electrolyte used by traditional lithium manganese battery manufacturing enterprises is mostly purchased outside, and independent research and development and design of the electrolyte in the aspect of safety performance are lacked, so that the battery manufactured by the purchased electrolyte has potential safety hazards of high working temperature, easy volatilization and decomposition of the electrolyte, flammability and explosion and the like; and fourthly, the battery has higher internal resistance due to unreasonable manufacturing process, the heat generated during the operation of the battery is increased, and the safety and stability of the battery are reduced.

Disclosure of Invention

The present invention aims to provide a high-safety disposable lithium manganese battery and a method for manufacturing the same, which solves one or more of the above-mentioned problems of the prior art.

In order to solve the technical problems, the invention provides a high-safety primary lithium-manganese battery, which comprises a positive plate, a negative plate, a ceramic diaphragm, electrolyte and a battery shell, wherein the positive plate, the ceramic diaphragm, the negative plate and the ceramic diaphragm are sequentially and repeatedly laminated to form a dry battery core, the primary lithium-manganese battery is prepared by putting the dry battery core into the battery shell and injecting the electrolyte, aging, sealing and aging, and the innovation points are as follows: the negative plate is electrochemically pre-doped with lithium, and a 'fully charged secondary lithium battery negative plate' or a 'zero-charged lithium/carbon half battery positive plate' is converted into a pre-lithiated negative plate, positive plate reserved lugs are arranged on the positive and negative surfaces of the positive plate, and negative plate reserved lugs are arranged on the positive and negative surfaces of the negative plate;

the dry cell comprises a positive electrode full tab and a negative electrode full tab, when a plurality of positive electrode sheets are laminated, the reserved tabs of the positive electrode sheets are mutually aligned and form a plurality of positive electrode sheet tabs, the plurality of positive electrode sheet tabs and the planar metal sheet current collector are welded to form a positive electrode full tab, when a plurality of negative electrode sheets are laminated, the reserved tabs of the negative electrode sheets are mutually aligned and form a plurality of negative electrode sheet tabs, and the plurality of negative electrode sheet tabs and the planar metal sheet current collector are welded to form a negative electrode full tab;

the ceramic diaphragm is a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability;

the electrolyte is prepared by mixing 0.7-2 mol of lithium salt and an organic solvent with high boiling point and low vapor pressure, wherein the organic solvent is carbonic ester or carboxylic ester;

the two ends of the battery shell are respectively provided with a shell anode current collector and a shell cathode current collector, the primary lithium manganese battery is placed into the battery shell by a dry battery core, and an anode full lug and a cathode full lug are respectively connected with the shell anode current collector and the shell cathode current collector and are manufactured by injecting electrolyte, aging, sealing and aging.

Further, the lithium salt is lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethyl (sulfonyl) imide, lithium trifluoromethyl (sulfonate) and lithium iodide;

the high boiling point and low vapor pressure carbonate is ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate;

the carboxylic ester with high boiling point and low vapor pressure is butyl acetate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone and delta-valerolactone.

Furthermore, the battery shell is square, and is made of steel, aluminum or aluminum plastic.

The invention provides a preparation method of a high-safety disposable lithium-manganese battery, which specifically comprises the following steps:

s1, preparing the manganese dioxide positive plate

Preparing anode material with the mass percent of 85-98%, conductive agent with the mass percent of 1-10% and binder with the mass percent of 1-15% into anode slurry, and uniformly coating the anode slurry on the front surface and the back surface of a current collector aluminum net, forming an anode coating on the front surface and the back surface of the current collector aluminum net by the anode slurry, reserving anode blank areas on four edges of the anode coating and four edges of the current collector aluminum net respectively, dividing the anode blank areas into anode sheet reserved lugs and 3 anode diaphragm wrapping areas, and positioning the anode sheet reserved lugs and one of the anode diaphragm wrapping areas at two ends of the anode coating, the other two anode diaphragm wrapping areas are positioned at the two sides of the anode coating, the current collector aluminum net coated with the anode coating is placed in a vacuum drying box, after being baked at 85 ℃ in a vacuum environment with-0.09 to-0.1 MPa, rolling the anode coating to a compact state by using a rolling device, wherein the surface density of the anode coating is 50-100 mg/cm.²Then baking the whole body at 110 ℃ in a vacuum environment of-0.09 to-0.1 MPa to obtain a manganese dioxide positive plate;

s2, preparing pre-lithiation negative plate

A. Preparing a spare pole piece: preparing a negative electrode material with the mass percentage of 85% -98%, 1% -10% of a conductive agent and 1% -15% of a binder into a negative electrode slurry, uniformly coating the negative electrode slurry on the front surface and the back surface of a current collector copper net, forming a negative electrode coating on the front surface and the back surface of the current collector copper net by the negative electrode slurry, reserving negative electrode blank areas on four edges of the negative electrode coating and four edges of the current collector copper net respectively, dividing the negative electrode blank areas into negative electrode sheet reserved lugs and 3 negative electrode diaphragm wrapping areas, reserving the negative electrode lugs and one of the negative electrode diaphragm wrapping areas at two ends of the negative electrode coating, and positioning the other two negative electrode diaphragm wrapping areas at two ends of the negative electrode coatingPlacing the current collector copper mesh coated with the negative coating on two sides of the negative coating in a vacuum drying box, baking at 85 ℃ in a vacuum environment of-0.09 to-0.1 MPa, and rolling to a compact state by using a calender to ensure that the surface density of the negative coating is 25-50 mg/cm²Then baking the whole body in a vacuum environment of-0.09 to-0.1 MPa at the temperature of 110 ℃ to obtain a spare pole piece;

B. preparing a secondary lithium battery: b, preparing the secondary lithium battery by using the spare pole piece obtained in the step A according to a conventional preparation process, wherein the spare pole piece becomes a negative pole piece of the secondary lithium battery;

C. preparation of lithium/carbon half-cells: b, preparing the spare pole piece obtained in the step A into a lithium/carbon half-cell according to a conventional preparation process, wherein the spare pole piece becomes a lithium/carbon half-cell positive plate;

D. preparing a pre-lithiated negative plate:

charging the secondary lithium battery in the step B fully, disassembling the secondary lithium battery in an inert gas atmosphere environment, and separating out a negative plate of the secondary lithium battery to obtain a pre-lithiated negative plate;

discharging the lithium/carbon half cell in the step C, disassembling the lithium/carbon half cell in an inert gas atmosphere environment, and separating out a positive plate of the lithium/carbon half cell to obtain a pre-lithiation negative plate;

s3 preparation of nano microporous ceramic diaphragm

Coating the front side and the back side of the ceramic diaphragm with a nano alumina coating, and removing a solvent in the alumina coating by means of a vacuum baking oven to obtain a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability, wherein the area of the nano microporous ceramic diaphragm is larger than that of a manganese dioxide positive plate or a pre-lithiation negative plate;

s4, preparing dry electric core

Combining and laminating a manganese dioxide positive plate, a nano micropore ceramic diaphragm, a pre-lithiation negative plate and a nano micropore ceramic diaphragm to form a dry battery cell; in the lamination process, 3 anode membrane wrapping areas are respectively wrapped by membranes, and reserved tabs of the anode plates are laminated and gathered together to form multiple anode tabs; 3 negative electrode diaphragm wrapping areas are respectively wrapped by diaphragms, and reserved tabs of the negative electrode plates are stacked and gathered together to form multiple negative electrode tabs; welding multiple positive electrode lugs and a planar metal sheet current collector to form positive electrode full lugs, and welding multiple negative electrode lugs and a planar metal sheet current collector to form negative electrode full lugs;

s5, assembling battery

And putting the dry battery cell into a battery shell at a certain temperature and under a certain pressure, respectively connecting a positive electrode full lug and a negative electrode full lug with a shell positive electrode current collector and a shell negative electrode current collector, injecting electrolyte, and then aging, sealing and aging to obtain the primary lithium manganese battery.

Further, the positive electrode material is manganese dioxide.

Further, the negative electrode material is one or a combination of more than two of mesocarbon microbeads, artificial graphite and a silicon-carbon composite material.

Further, the current collector aluminum mesh is an aluminum mesh with high porosity and the thickness of the current collector aluminum mesh is 10-25 um; the mass flow body copper mesh is the copper product net piece of high porosity, and thickness is 6 ~ 20 um.

Further, the conductive agent is one or a combination of more than two of superconducting carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is one or the combination of more than two of polyvinylidene fluoride, styrene butadiene rubber and sodium carboxymethyl cellulose.

The invention has the beneficial effects that:

1. the carbon-based negative plate pre-doped with lithium is preferably selected to replace a metal lithium negative plate, the carbon material has the characteristics of stable structure, high electronic conductivity, multiple pore canals, large pore volume, strong adsorption capacity and the like, and is used as a carrier material of lithium ions to provide more output channels for migration of the lithium ions, so that the lithium ions are more uniformly dispersed in the pore canals, the enrichment of the lithium ions is reduced, the utilization rate of the lithium ions is improved, when the interior of the battery is exposed in the air, the porous structure of the carbon adsorbs the lithium ions in the pore canals, the precipitation of the lithium ions is inhibited, the contact between the lithium ions and the air is weakened, and the safety and stability of the battery are improved.

2. By optimizing the nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability, the nano alumina ceramic coating on the surface of the diaphragm improves the affinity of the diaphragm with electrolyte, provides more pore channels for the migration and transmission of lithium ions, improves the melting point of the diaphragm, strengthens the hardness of the surface of the diaphragm, and reduces the risk of hard-strength active substances and hairs piercing the diaphragm; when the interior of the battery is exposed in the air, the ceramic diaphragm absorbs lithium ions and electrolyte, so that the direct contact of the lithium ions and the electrolyte with the air is greatly reduced, the occurrence of chemical reaction is slowed down, the ignition, the deflagration and the explosion of the battery are effectively prevented, and the safety and the stability of the battery are improved.

3. The organic solvent of the electrolyte is preferably selected from solvents with high boiling point, low melting point and low vapor pressure, the boiling point of the solvents is 120-240 ℃, the melting point of the solvents is-40-100 ℃, the higher boiling point reduces the evaporability of the solvents, reduces the volatilization of the electrolyte, avoids dry regions in the battery, the lower melting point improves the low-temperature fluidity of the electrolyte, widens the working temperature range of the battery, and effectively slows down the decomposition reaction of the electrolyte due to the characteristics of high boiling point and low vapor pressure when the interior of the battery is exposed to the air, thereby improving the safety and stability of the battery.

4. Through preferably selecting the preparation process of taking the positive/negative active material and the current collector mesh sheets with reserved lugs in a coating and rolling mode as the positive/negative plate, the contact area of the active material and the current collector is increased, the compactness of the active material is improved, the lugs reserved in each current collector mesh sheet are stacked and gathered and then welded to form the full lugs to reduce the internal resistance of the battery, the heat generated during the operation of the battery is weakened, and the safety and stability of the battery are improved.

Drawings

Fig. 1 is a cross-sectional view of the surface of an aluminum mesh for current collectors of the present invention.

Fig. 2 is a cross-sectional view of the surface of the current collector copper mesh of the present invention.

Fig. 3 is a cross-sectional side view of a stack of dry cells of the present invention.

Fig. 4 is a schematic side view of a primary lithium manganese battery according to the present invention.

Fig. 5 is a graph showing the mass energy density of the primary lithium manganese battery according to the present invention.

Detailed Description

As shown in fig. 1 to 4, a high-safety primary lithium-manganese battery comprises a positive plate 1, a negative plate 2, a ceramic diaphragm 3, an electrolyte and a battery case 4, wherein the positive plate 1, the ceramic diaphragm 3, the negative plate 2 and the ceramic diaphragm 3 are sequentially and repeatedly laminated to form a dry battery core, the primary lithium-manganese battery is manufactured by putting the dry battery core into the battery case 4 and injecting the electrolyte, aging, sealing and aging, the negative plate is electrochemically pre-doped with lithium, so that a "full-charge state negative plate of a secondary lithium battery" or a "zero-charge state positive plate of a lithium/carbon half-battery" is converted into a pre-lithiation negative plate 2, positive plate reserved tabs 11 are arranged on both sides of the positive plate 1, and negative plate reserved tabs 21 are arranged on both sides of the negative plate 2;

the dry cell comprises a positive electrode full tab and a negative electrode full tab, when a plurality of positive electrode sheets 1 are laminated, the reserved tabs 11 of the positive electrode sheets are mutually aligned and form a plurality of positive electrode sheet tabs, the plurality of positive electrode sheet tabs and the planar metal sheet current collector are welded to form a positive electrode full tab, when a plurality of negative electrode sheets 2 are laminated, the reserved tabs 21 of the negative electrode sheets are mutually aligned and form a plurality of negative electrode sheet tabs, and the plurality of negative electrode sheet tabs and the planar metal sheet current collector are welded to form a negative electrode full tab;

the ceramic diaphragm 3 is a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability;

the electrolyte is prepared by mixing 0.7-2 mol of lithium salt and an organic solvent with high boiling point and low vapor pressure, wherein the organic solvent is carbonic ester or carboxylic ester;

the two ends of the battery case 4 are respectively provided with a case anode current collector 41 and a case cathode current collector 42, the primary lithium manganese battery is placed in the battery case 4 by a dry battery core, and the anode full tab and the cathode full tab are respectively connected with the case anode current collector 41 and the case cathode current collector 42, and the primary lithium manganese battery is manufactured by injecting electrolyte, aging, sealing and aging.

In the invention, the lithium salt is lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (fluorosulfonyl) imide, lithium trifluoromethyl (sulfonyl) sulfonate and lithium iodide;

the high boiling point and low vapor pressure carbonate is ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate;

the carboxylic ester with high boiling point and low vapor pressure is butyl acetate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone and delta-valerolactone.

In the present invention, the battery case 4 is square, and the material of the battery case 4 is steel, aluminum, or aluminum plastic.

The invention provides a preparation method of a high-safety disposable lithium-manganese battery, which specifically comprises the following steps:

s1, preparing the manganese dioxide positive plate

Preparing anode material with the mass percent of 85-98%, conductive agent with the mass percent of 1-10% and binder with the mass percent of 1-15% into anode slurry, and uniformly coating the anode slurry on the front and back surfaces of a current collector aluminum net 101, wherein the anode slurry forms an anode coating 14 on the front and back surfaces of the current collector aluminum net 101, four edges of the anode coating 14 respectively reserve anode blank areas with four edges of the current collector aluminum net 101, the anode blank areas are divided into anode sheet reserved lugs 11 and 3 anode diaphragm wrapping areas 12, the anode sheet reserved lugs 11 and one of the anode diaphragm wrapping areas 12 are positioned at two ends of the anode coating 14, the other two anode diaphragm wrapping areas 12 are positioned at two sides of the anode coating 14, the current collector aluminum net 101 coated with the anode coating 14 is placed in a vacuum drying box, after being baked at 85 ℃ in a vacuum environment with-0.09 to-0.1 MPa, rolling the mixture to a compact state by using a rolling device, wherein the surface density of the positive electrode coating 14 is 50-100 mg/cm.²Then baking the whole body at 110 ℃ in a vacuum environment of-0.09 to-0.1 MPa to obtain a manganese dioxide positive plate;

s2, preparing pre-lithiation negative plate

A. Preparing a spare pole piece: preparing a negative electrode slurry from 85-98% of a negative electrode material, 1-10% of a conductive agent and 1-15% of a binder by mass percent, uniformly coating the negative electrode slurry on the front surface and the back surface of a current collector copper mesh 102, and coating the negative electrode slurry on the front surface and the back surface of the current collector copper mesh 102Forming negative electrode coatings 24 on the front surface and the back surface of a current collector copper net 102 by using slurry, reserving negative electrode blank areas on four edges of the negative electrode coatings 24 and four edges of the current collector copper net 102 respectively, dividing the negative electrode blank areas into negative electrode sheet reserved lugs 21 and 3 negative electrode diaphragm wrapping areas 22, arranging the negative electrode sheet reserved lugs 21 and one of the negative electrode diaphragm wrapping areas 22 at two ends of the negative electrode coatings 24, arranging the other two negative electrode diaphragm wrapping areas 22 at two sides of the negative electrode coatings 24, placing the current collector copper net 102 coated with the negative electrode coatings 24 in a vacuum drying box, baking at 85 ℃ in a vacuum environment of-0.09 to-0.1 MPa, rolling to a compact state by using a rolling device, and enabling the surface density of the negative electrode coatings 24 to be 25-50 mg/cm²Then baking the whole body in a vacuum environment of-0.09 to-0.1 MPa at the temperature of 110 ℃ to obtain a spare pole piece;

B. preparing a secondary lithium battery: b, preparing the secondary lithium battery by using the spare pole piece obtained in the step A according to a conventional preparation process, wherein the spare pole piece becomes a negative pole piece of the secondary lithium battery;

C. preparation of lithium/carbon half-cells: b, preparing the spare pole piece obtained in the step A into a lithium/carbon half-cell according to a conventional preparation process, wherein the spare pole piece becomes a lithium/carbon half-cell positive plate;

D. preparing a pre-lithiated negative plate 2:

charging the secondary lithium battery in the step B fully, disassembling the secondary lithium battery in an inert gas atmosphere environment, and separating out a negative plate of the secondary lithium battery to obtain a pre-lithiated negative plate 2;

discharging the lithium/carbon half cell in the step C, disassembling the lithium/carbon half cell in an inert gas atmosphere environment, and separating out a positive plate of the lithium/carbon half cell to obtain a pre-lithiation negative plate 2;

s3 preparation of nano microporous ceramic diaphragm

Coating the front side and the back side of the ceramic diaphragm 3 with a nano alumina coating, and removing a solvent in the alumina coating by means of a vacuum baking oven to obtain a nano microporous ceramic diaphragm with high mechanical strength, high porosity and high wettability, wherein the area of the nano microporous ceramic diaphragm is larger than that of a manganese dioxide positive plate or a pre-lithiation negative plate;

s4, preparing dry electric core

Combining and laminating a manganese dioxide positive plate, a nano micropore ceramic diaphragm, a pre-lithiation negative plate and a nano micropore ceramic diaphragm to form a dry battery cell; in the lamination process, 3 anode membrane wrapping areas 12 are respectively wrapped by membranes 103, and the reserved tabs 11 of the anode plates are laminated and gathered together to form multiple anode tabs; 3 negative electrode diaphragm wrapping areas 22 are respectively wrapped by diaphragms 103, and the reserved tabs 21 of the negative electrode sheets are stacked and gathered together to form multiple negative electrode tabs; welding multiple positive electrode lugs and a planar metal sheet current collector to form positive electrode full lugs, and welding multiple negative electrode lugs and a planar metal sheet current collector to form negative electrode full lugs;

s5, assembling battery

And putting the dry cell into a cell shell 4 at a certain temperature and under a certain pressure, respectively connecting a positive electrode full lug and a negative electrode full lug with a shell positive electrode current collector 41 and a shell negative electrode current collector 42, injecting electrolyte, and then aging, sealing and aging to obtain the primary lithium manganese cell.

In the present invention, the positive electrode material is manganese dioxide.

In the invention, the negative electrode material is one or a combination of more than two of mesocarbon microbeads, artificial graphite and a silicon-carbon composite material.

In the invention, the current collector aluminum mesh 101 is an aluminum mesh with high porosity and the thickness is 10-25 um; the current collector copper mesh 102 is a copper mesh with high porosity and is 6-20 um thick.

In the invention, the conductive agent is one or the combination of more than two of superconducting carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is one or the combination of more than two of polyvinylidene fluoride, styrene butadiene rubber and sodium carboxymethyl cellulose.

FIG. 5 is a graph showing the mass energy density of the primary lithium manganese dioxide battery according to the present invention, wherein the mass energy density is more than 500 wh/kg.

The prepared primary lithium manganese battery has no phenomena of fire, deflagration and explosion after the tests of impact, extrusion and needling, and has higher safety performance than the traditional primary lithium manganese battery.

It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.